Cyclic Copper Uptake and Release from Natural Seawater-A Fully Sustainable Antifouling Technique to Prevent Marine Growth.

Unwanted growth of fouling organisms on underwater surfaces is an omnipresent challenge for the marine industry, costing billions of dollars every year in the transportation sector alone. Copper, the most widely used biocide in antifouling paints, is at the brink of a total ban in being used in antifouling coatings, as it has become an existential threat to nontargeted species due to anthropogenic copper inputs into protected waters. In the current study, using a porous and cross-linked poly(ethylene imine) structure under marine and fouling environments, available copper from natural seawater was absorbed and electrochemically released back as a potent biocide at 1.3 V vs Ag|AgCl, reducing marine growth by 94% compared to the control electrode (coupon) at 0 V. The coating can also function as an electrochemical copper sensor enabling real-time monitoring of the electrochemical uptake and release of copper ions from natural seawater. This allows tailoring of the electrochemical program to the changing marine environments, i.e., when the vessels move from high-copper-contaminated waters to coastal regions with low concentrations of copper.

Fluorescence recovery after photobleaching in material and life sciences: putting theory into practice.

Fluorescence recovery after photobleaching (FRAP) is a versatile tool for determining diffusion and interaction/binding properties in biological and material sciences. An understanding of the mechanisms controlling the diffusion requires a deep understanding of structure-interaction-diffusion relationships. In cell biology, for instance, this applies to the movement of proteins and lipids in the plasma membrane, cytoplasm and nucleus. In industrial applications related to pharmaceutics, foods, textiles, hygiene products and cosmetics, the diffusion of solutes and solvent molecules contributes strongly to the properties and functionality of the final product. All these systems are heterogeneous, and accurate quantification of the mass transport processes at the local level is therefore essential to the understanding of the properties of soft (bio)materials. FRAP is a commonly used fluorescence microscopy-based technique to determine local molecular transport at the micrometer scale. A brief high-intensity laser pulse is locally applied to the sample, causing substantial photobleaching of the fluorescent molecules within the illuminated area. This causes a local concentration gradient of fluorescent molecules, leading to diffusional influx of intact fluorophores from the local surroundings into the bleached area. Quantitative information on the molecular transport can be extracted from the time evolution of the fluorescence recovery in the bleached area using a suitable model. A multitude of FRAP models has been developed over the years, each based on specific assumptions. This makes it challenging for the non-specialist to decide which model is best suited for a particular application. Furthermore, there are many subtleties in performing accurate FRAP experiments. For these reasons, this review aims to provide an extensive tutorial covering the essential theoretical and practical aspects so as to enable accurate quantitative FRAP experiments for molecular transport measurements in soft (bio)materials.

Unhindered copper uptake by glutaraldehyde-polyethyleneimine coatings in an artificial seawater model system with adsorbed swollen polysaccharides and competing ligand EDTA.

Shortly after a surface is submerged in the sea, a conditioning film is generally formed by adsorption of organic molecules, such as polysaccharides. This could affect transport of molecules and ions between the seawater and the surface. An artificial seawater model system was developed to understand how adsorbed polysaccharides impact copper binding by glutaraldehyde-crosslinked polyethyleneimine coatings. Coating performance was also determined when competed against copper-chelating EDTA. Polysaccharide adsorption and copper binding and distribution were investigated using advanced analytical techniques, including depth-resolved time-of-flight secondary ion mass spectroscopy, grazing incidence X-ray absorption near-edge spectroscopy, quartz crystal microbalance with dissipation monitoring and X-ray photoelectron spectroscopy. In artificial seawater, the polysaccharides adsorbed in a swollen state that copper readily penetrated and the glutaraldehyde-polyethyleneimine coatings outcompeted EDTA for copper binding. Furthermore, the depth distribution of copper species was determined with nanometre precision. The results are highly relevant for copper-binding and copper-releasing materials in seawater.

Correction: Magnetically induced structural anisotropy in binary colloidal gels and its effect on diffusion and pressure driven permeability.

Correction for 'Magnetically induced structural anisotropy in binary colloidal gels and its effect on diffusion and pressure driven permeability' by Christoffer Abrahamsson et al., Soft Matter, 2014, 10, 4403-4412.

Cu(I) stabilizing crosslinked polyethyleneimine.

Polyethyleneimine (PEI) is known for its metal-coordinating properties and in its crosslinked form has applications in different areas ranging from drug delivery to waste water treatment and recovery of trace metals. With the aim to regulate the coordination environment of Cu(I) and Cu(II) ions in marine coatings, we have prepared a triazole cross-linking agent with 'soft' coordination that can crosslink PEI via indirect reductive amination. We have shown that this triazole crosslinker not only increases the Cu(II) absorption capacity of the crosslinked PEI in comparison to the traditionally used glutaraldehyde-crosslinked PEI (PEI-GA), but also allows the crosslinked polymer network to stabilize the Cu(I) oxidation state more effectively. The Cu(II) uptake and Cu(I) stabilization of the polymer have been determined by elemental analysis and UV-vis spectroscopy. It was found that the triazole-crosslinked polymer (PEI-TA) could coordinate up to 12 wt% of Cu(II) before and 6 wt% Cu(II) after imine reduction.

Magnetically induced structural anisotropy in binary colloidal gels and its effect on diffusion and pressure driven permeability.

We report on the synthesis, microstructure and mass transport properties of a colloidal hydrogel self-assembled from a mixture of colloidal silica and nontronite clay plates at different particle concentrations. The gel-structure had uniaxial long-range anisotropy caused by alignment of the clay particles in a strong external magnetic field. After gelation the colloidal silica covered the clay particle network, fixing the orientation of the clay plates. Comparing gels with a clay concentration between 0 and 0.7 vol%, the magnetically oriented gels had a maximum water permeability and self-diffusion coefficient at 0.3 and 0.7 vol% clay, respectively. Hence the specific clay concentration resulting in the highest liquid flux was pressure dependent. This study gives new insight into the effect of anisotropy, particle concentration and bound water on mass transport properties in nano/microporous materials. Such findings merit consideration when designing porous composite materials for use in for example fuel cell, chromatography and membrane technology.

Encapsulation of actives for sustained release.

Encapsulation of actives in miniature reservoirs, called microcapsules, is used for protection and in particular controlled release of the active. Regarding controlled release applications, the most common function of the microcapsule is to sustain or extend the release of the active. A number of encapsulation methodologies are available including; internal phase separation, interfacial polymerization, formation of multiple emulsions, Layer-by-Layer adsorption of polyelectrolytes and soft templating techniques, all of which are reviewed in this Perspective. The choice of method depends on the nature of the active (hydrophilic/hydrophobic, size, physical state) and on the intended release rate and release profile. Ways to manipulate the release of the active by tailoring the physicochemical properties of the microcapsule are reviewed. Moreover, appropriate diffusion models are introduced to describe the release profile from a variety of microcapsule morphologies, including Fickian diffusion models and Brownian motion, and the meaning and the misuse of the term "zero-order release" are briefly discussed.

Charged microcapsules for controlled release of hydrophobic actives. Part III: the effect of polyelectrolyte brush- and multilayers on sustained release.

Poly(methyl methacrylate) microspheres have been prepared by the internal phase separation method using either of the three conventional dispersants poly(vinyl alcohol) (PVA), poly(methacrylic acid) (PMAA), or the amphiphilic block copolymer poly(methyl methacrylate)-block-poly(sodium methacrylate). The block copolymer based microsphere, which has a polyelectrolyte brush on the surface, was surface modified with up to two poly(diallyldimethylammonium chloride)-poly(sodium methacrylate) bilayers. The microspheres were loaded with the hydrophobic dye 2-(4-(2-chloro-4-nitrophenylazo)-N-ethylphenylamino)ethanol (Disperse Red 13) and its release from aqueous dispersions of microspheres with the different surface compositions was measured by spectrophotometry. The burst fraction, burst rate and the diffusion constant were determined from a model combining burst and diffusive release. Out of the three dispersants, the block copolymer gave the slowest release of the dye, with respect to both burst release and diffusive release. A very pronounced further reduction of the diffusion constant was obtained by applying polyelectrolyte multilayers on top of the microspheres. However, the diffusion constant was very weakly dependent on further polyelectrolyte adsorption and one polyelectrolyte bilayer appeared to suffice.

The importance of proper anchoring of an amphiphilic dispersant for colloidal stability.

Highly stable poly(methyl methacrylate) (PMMA) based microcapsule suspensions without excess dispersant are obtained via the solvent evaporation route using poly(methyl methacrylate)-block-poly(sodium methacrylate) or poly(methyl methacrylate)-block-poly(sodium acrylate) diblock copolymers as dispersant. The stable suspension is characterized by a high ζ-potential that does not change with time or after washing steps. It is indirectly proven on model PMMA surfaces using quartz crystal microbalance with dissipation monitoring that the PMMA block of the copolymer is embedded in the underlying PMMA microcapsule. Such anchoring of the dispersant is key for the good colloidal stability.

Structure, diffusion, and permeability of protein-stabilized monodispersed oil in water emulsions and their gels: a self-diffusion NMR study.

Self-diffusion NMR is used to investigate monodispersed oil in water emulsions and the subsequent gel formed by removing the water through evaporation. The radius of the oil droplets in the emulsions is measured using a number of diffusion methods based on the measurement of the mean squared displacement of the oil, water, and tracer molecules. The results are consistent with the known size of the emulsions. Bragg-like reflections due to the restricted diffusion of the water around the oil droplets are observed due to the low polydispersity of the emulsions and the dense packing. The resulting data are fitted to a pore glass model to give the diameter of both the pools of interstitial water and the oil droplets. In the gel, information on the residual three-dimensional structure is obtained using the short time behavior of the effective diffusion coefficient to give the surface to volume ratio of the residual protein network structure. The values for the surface to volume ratio are found to be consistent with the expected increase of the surface area of monodisperse droplets forming a gel network. At long diffusion observation times, the permeability of the network structure is investigated by diffusion NMR to give a complete picture of the colloidal system considered.

Coordination of imidazoles by Cu(II) and Zn(II) as studied by NMR relaxometry, EPR, far-FTIR vibrational spectroscopy and ab initio calculations: effect of methyl substitution.

Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position.

Dissolution and gelation of cellulose in TBAF/DMSO solutions: the roles of fluoride ions and water.

Solutions of cellulose in a mixture of tetrabutylammonium fluoride and dimethyl sulfoxide (TBAF/DMSO) containing small and varying amounts of water were studied by nuclear magnetic resonance (NMR). By measuring the composition dependences of (19)F NMR and (1)H NMR chemical shifts and line widths, details on the dissolution and gelation mechanisms for cellulose in TBAF/DMSO were elucidated. Our results suggest that the strongly electronegative fluoride ions act as hydrogen bond acceptors to cellulose hydroxyl groups, thus dissolving the polymer by breaking the cellulose-cellulose hydrogen bonds and by rendering the chains an effective negative charge. It was found that the fluoride ions also interact strongly with water. Small amounts of water remove the fluoride ions from the cellulose chains and allow reformation of the cellulose-cellulose hydrogen bonds, which leads to formation of highly viscous solutions or gels even at low cellulose concentrations.

Dendrimer diffusion in kappa-carrageenan gel structures.

The effect of the kappa-carrageenan concentration on gel microstructure and self-diffusion of polyamideamine dendrimers has been determined by transmission electron microscopy (TEM), image analysis, and nuclear magnetic resonance (NMR) diffusometry. Different salt conditions of KCl, NaCl, and mixtures thereof allowed for formation of significantly different microstructures. The kappa-carrageenan concentrations were varied between 0.25 and 3.0 w/w% for a salt mixture containing 20 mM KCl and 200 mM NaCl gels and between 0.5 and 4.0 w/w% for 250 mM NaCl gels. Furthermore, the effect of potassium ion concentration on the gel structure and the dendrimer diffusion rate was determined. The potassium ion concentration was varied between 20 mM KCl and 200 mM KCl. Two different dendrimer generations with significant difference in size were used: G2 and G6. Dendrimers were found to be sensitive probes for determination of the effect of the gel microstructure on molecular diffusion rate. A qualitative comparison between TEM micrographs, NMR diffusometry data and image analysis showed that the gel structure has a large impact on the dendrimers diffusion in kappa-carrageenan gels. It was found that diffusion was strongly influenced by the kappa-carrageenan concentration and the dendrimer generation. Small voids in the gel network gave strongly reduced diffusion. Image analysis revealed that the interfacial area between the gel network and the surrounding water phase correlated well with the dendrimer diffusion.

Brownian dynamics simulations in hydrogels using an adaptive time-stepping algorithm.

The adaptive time-stepping algorithm for Brownian simulation of solute diffusion in three-dimensional complex geometries previously developed by the authors of this paper was applied to heterogeneous three-dimensional polymer hydrogel structures. The simulations were performed on reconstructed three-dimensional hydrogels. The obstruction effect from the gel strands on water and diffusion of dendrimers with different sizes were determined by simulations and compared with experimental nuclear magnetic resonance diffusometry data obtained from the same material. It was concluded that obstruction alone cannot explain the observed diffusion rates, but an interaction between the dendrimers and the gel strands should be included in the simulations. The effect of a sticky-wall interaction potential with geometrically distributed residence times on the diffusion rate has been studied. It was found that sticky-wall interaction is a possible explanation for the discrepancy between simulated and experimental diffusion data for dendrimers of different sizes diffusing in hydrogels.

Towards a biosensor immunoassay of protein-bound isopeptides in human plasma.

This study demonstrates that synthetic isopeptides formed on BSA can be quantitatively analyzed by a surface plasmon resonance-based biosensor method. A monoclonal IgM antibody 81D4, that reacts with the synthetic isopeptide and also with the natural isopeptide cross-link in D-dimer (but not with its non-cross-linked fibrin monomer), was covalently immobilized to a carboxymethylated dextran surface, a CM5 surface. Its immunocapturing efficiency was found to be good. The affinity of the interaction between the monoclonal 81D4 and the synthetic isopeptide was estimated to approximately 4x10(-7)M. Good reactivity was also observed when human plasma spiked with this isopeptide was used as test solution. Cross-linked D-dimer in the plasma of patients is a marker of disseminated intravascular coagulation (DIC) which occurs late in sepsis. This biosensor method has the potential to be developed into a rapid sensitive assay for measuring the level of natural isopeptide cross-links in proteins in the plasma of patients with a suspected diagnosis of sepsis.

Structure and dynamics of a sponge phase in the methyl delta-aminolevulinate/monoolein/water/propylene glycol system.

The structural effect caused by the addition of up to 16% (w/w) of the hydrochloride salt of delta-aminolevulinic acid (ALA, HOOC-CH2-CH2-CO-CH2-NH2HCl) or its methyl ester (m-ALA) to the sponge phase formed of monoolein/water/propylene glycol was investigated by means of crossed polarizers, small angle X-ray diffraction (SAXD) and nuclear magnetic resonance diffusometry (NMRD). Inspection with crossed polarizers revealed that additions of 4-16% (w/w) m-ALA transformed the isotropic bicontinuous sponge phase partly (4-10%) or completely (13 and 16%) into an anisotropic lamellar phase, indicating that m-ALA has a flattening effect on the bilayer curvature. The addition of 16% (w/w) ALA did not show any effect on the sponge phase. By addition of water to the anisotropic m-ALA samples, isotropic liquids were re-formed. The SAXD data for the isotropic liquids showed a diffuse Bragg peak and the NMRD self-diffusion coefficients for the drug (m-ALA) and the components of the original sponge phase (monoolein, water and propylene glycol) were shown to be essentially constant for 0-16% (w/w) added m-ALA. These results confirmed the hypothesis that the re-formed isotropic phases were indeed sponge phases. Water, for example, showed a diffusion coefficient of 3.1-3.9x10(-10)m(2)s(-1) in the sponge phase, compared to 5.3-5.7 x 10(-10)m2s(-1) in relevant water/propylene glycol solutions or 2.3 x 10(-9)m2s(-1) in pure water. The reduction can be explained as a consequence of the microstructure (congruent monoolein bilayer) of the sponge phase and of the viscosity effect caused by propylene glycol and m-ALA.

Copper removal from acid mine drainage-polluted water using glutaraldehyde-polyethyleneimine modified diatomaceous earth particles.

Mine waters and tailings generated from mining and mineral processing activities often have detrimental impact on the local environment. One example is acid mine drainage, in which sulphides in the mining waste react with water and oxygen to produce an acidic environment that subsequently dissolves host rock minerals from the waste containing toxic metals and trace elements. Copper is one such metal of significance, as it is mined at large volumes in sulphide containing ores. It has strong biocidal activity that greatly affects ecosystems. We have previously reported that glutaraldehyde (GA)-crosslinked polyethyleneimine (PEI) has strong affinity and selectivity for copper and that diatomaceous earth (DE) particles can be modified with the material to form a copper-extraction resin. In this study, the copper uptake of GA-PEI-DE particles was investigated from synthetic and real acid mine drainage samples under different pHs and their copper removal performance was compared with that of selected commercial resins. The results revealed that copper could effectively and preferentially bind to the material at pH 4, and that the copper could be completely eluted by lowering of the pH. In addition, effective copper uptake and elution was demonstrated using real legacy acid mine drainage water from Mount Lyell in Tasmania.

Bio-template assisted synthesis of porous glutaraldehyde-polyethyleneimine particulate resin for selective copper ion binding and recovery.

Porous ion-exchange resins with features of high selectivity, high capacity, fast adsorption kinetics and chemical stability over a wide pH range are attractive for extracting precious metals like copper and upcycling waste. In this study, porous glutaraldehyde-polyethyleneimine (GA-PEI) particulate resin was synthesised using diatomaceous earth (DE) particles as a bio-template. The crosslinking of PEI by GA was successfully conducted on the surface of DE. Removal of the template DE, merely by chemical etching with potassium hydroxide, resulted in the porous GA-PEI particulate resin. The resin showed excellent selectivity for copper ions in binding and recovery from solutions as complex as real legacy acid mine drainage liquid. The copper ion uptake capacity of the GA-PEI resin was determined to be >8 times greater than non-etched GA-PEI-DE particles. Under the investigated conditions, the GA-PEI resin showed higher selectivity to copper ions from real legacy acid mine drainage liquid compared to the commercial resins Purolite S930 Plus and Lewatit TP 220. Importantly, the absorbed copper ions could be released by simply adjusting pH of the solution to 1. For uptake from acid mine drainage liquid at pH 4 and elution at pH 1, purer copper solutions were achieved with GA-PEI compared to Purolite S930 Plus or Lewatit TP 220 following two cycles of iteration. The results indicate the great potential for using the porous GA-PEI resin in copper extraction under real-world conditions.

Scaling exponent and dispersity of polymers in solution by diffusion NMR.

Molecular mass distribution measurements by pulsed gradient spin echo nuclear magnetic resonance (PGSE NMR) spectroscopy currently require prior knowledge of scaling parameters to convert from polymer self-diffusion coefficient to molecular mass. Reversing the problem, we utilize the scaling relation as prior knowledge to uncover the scaling exponent from within the PGSE data. Thus, the scaling exponent-a measure of polymer conformation and solvent quality-and the dispersity (Mw/Mn) are obtainable from one simple PGSE experiment. The method utilizes constraints and parametric distribution models in a two-step fitting routine involving first the mass-weighted signal and second the number-weighted signal. The method is developed using lognormal and gamma distribution models and tested on experimental PGSE attenuation of the terminal methylene signal and on the sum of all methylene signals of polyethylene glycol in D2O. Scaling exponent and dispersity estimates agree with known values in the majority of instances, leading to the potential application of the method to polymers for which characterization is not possible with alternative techniques.

Electroactive Polyhydroquinone Coatings for Marine Fouling Prevention-A Rejected Dynamic pH Hypothesis and a Deceiving Artifact in Electrochemical Antifouling Testing.

Nanometer-thin coatings of polyhydroquinone (PHQ), which release and absorb protons upon oxidation and reduction, respectively, were tested for electrochemically induced anti-biofouling activity under the hypothesis that a dynamic pH environment would discourage fouling. Antifouling tests in artificial seawater using the marine, biofilm-forming bacterium Vibrio alginolyticus proved the coatings to be ineffective in fouling prevention but revealed a deceiving artifact from the reactive species generated at the counter electrode (CE), even for electrochemical bias potentials as low as |400| mV versus Ag|AgCl. These findings provide valuable information on the preparation of nanothin PHQ coatings and their electrochemical behavior in artificial seawater. The results further demonstrate that it is critical to isolate the CE in electrochemical anti-biofouling testing.