A new hierarchical model for the electrodialysis (ED) process is presented. The model has been implemented into gPROMs Modelbuilder (PSE), allowing the development of a distributed-parameters simulation tool that combines the effectiveness of a semi-empirical modelling approach to the flexibility of a layered arrangement of modelling scales. Thanks to its structure, the tool makes possible the simulation of many different and complex layouts, requiring only membrane properties as input parameters (e.g. membrane resistance or salt and water permeability). The model has been validated against original experimental data obtained from a lab scale ED test rig. Simulation results concerning a 4-stage treatment of seawater and dynamic batch operations of brackish water desalination are presented, showing how the model can be effectively used for predictive purposes and for providing useful insights on design and optimisation.

We demonstrate that dopamine is able to self-polymerize and adhere firmly onto the substrate, which can create a hierarchical structure comprising an ultrathin active layer and a porous support layer. Such an approach opens a novel way to fabricating highly efficient and stable composite materials including composite membranes. More specifically, in this study the composite membranes are fabricated by simply dipping microporous substrate in aqueous dopamine solution under mild conditions. Nanoindentation measurement reveals the tight adhesion of dopamine onto microporous substrate, which is ascribed to numerous pi-pi and hydrogen-bonding interactions. The chemical composition of the active layer is analyzed by XPS, which demonstrates the self-polymerization of dopamine. The water contact angle of the dopamine coated membranes is reduced remarkably compared with that of the uncoated counterpart. Stylus profiler measurements display that the poly(dopamine) thickness increases as the coating time increases. FESEM images of the membranes' cross section show that an active layer (<100 nm) is deposited on the porous polysulfone (PS) substrate. Positron annihilation spectroscopy (PAS) is introduced to probe the fractional free volume properties throughout the cross section of the composite membranes and reveal that after dopamine double-coating the active layer becomes thicker and more compact. Moreover, pH and concentration of the dopamine solution exert notable influence on the fractional free volume of the composite membranes. The as-prepared membranes are tentatively employed for pervaporative desulfurization and exhibits satisfying separation performance as well as durability. This facile, versatile, and efficient approach enables a promising prospect for the wide applications of such novel kinds of ultrathin composite materials.

We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we used dopamine self-polymerization to form thin, surface-adherent polydopamine films onto a wide range of inorganic and organic materials, including noble metals, oxides, polymers, semiconductors, and ceramics. Secondary reactions can be used to create a variety of ad-layers, including self-assembled monolayers through deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioinert and bioactive surfaces via grafting of macromolecules.

The deposition of "polydopamine" films, from an aqueous solution containing dopamine or other catecholamines, constitutes a new and versatile way to functionalize solid-liquid interfaces. Indeed such films can be deposited on almost all kinds of materials. Their deposition kinetics does not depend markedly on the surface chemistry of the substrate, and the films can reach thickness of a few tens of nanometers in a single reaction step. Up to now, even if a lot is known about the oxidation mechanism of dopamine in solution, only little information is available to describe the deposition mechanism on surfaces either by oxidation in solution or by electrodeposition. The deposition kinetics of melanin was only investigated from dopamine solutions using oxygen or ammonium persulfate as an oxidant and from a tris(hydroxymethyl) aminomethane (Tris) containing buffer solutions at pH 8.5. Many other oxidants could be used, and the buffer agent containing a primary amine group may influence the deposition process. Herein we show that the deposition kinetics of melanin from dopamine containing buffers at pH 8.5 can be markedly modified using Cu(2+) instead of O2 as an oxidant: the deposition kinetics remains linear up to thicknesses of more than 70 nm, whereas the film growth stops at 45 ± 5 nm in the presence of 02. In addition, the films prepared from Cu(2+) containing solutions display an absorption spectrum with defined peaks at 320 and 370 nm, which are absent in the spectra of films prepared in oxygenated solutions. The replacement of Tris buffer by phosphate buffer also has a marked effect on the melanin deposition kinetics.

Mussel-inspired polydopamine (PDA) deposition offers a promising route to fabricate multifunctional coatings for various materials. However, PDA deposition is generally a time-consuming process, and PDA coatings are unstable in acidic and alkaline media, as well as in polar organic solvents. We report a strategy to realize the rapid deposition of PDA by using CuSO4/H2O2 as a trigger. Compared to the conventional processes, our strategy shows the fastest deposition rate reported to date, and the PDA coatings exhibit high uniformity and enhanced stability. Furthermore, the PDA-coated porous membranes have excellent hydrophilicity, anti-oxidant properties, and antibacterial performance. This work demonstrates a useful method for the environmentally friendly, cost-effective, and time-saving fabrication of PDA coatings.© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Fe(III)-coordination chemistry of neuromelanin building-block compounds, 5,6-dihydroxyindole (DHI), 5,6-dihydroxyindole-2-carboxylic acid (DHICA), and 5,6-dihydroxy-N-methyl-indole (Me-DHI), and the neurotransmitter dopamine were explored in aqueous solution by anaerobic pH-dependent spectrophotometric titrations. The Fe(III)-binding constants and pH-dependent speciation parallel those of catechol in that mono, bis, and tris FeLx species are present at concentrations dependent on the pH. The bis FeL2 dihydroxyindole species are favorable for L = DHI and DHICA under neutral to mildly acidic conditions. DHI and DHICA are stronger Fe(III) chelates than catechol, dopamine, and Me-DHI at pH values from 3 to 10. Oxidation studies reveal that iron accelerates the air oxidation of DHI and DHICA.

This study aims to explore the fundamental surface characteristics of polydopamine (pDA)-coated hydrophobic polymer films. A poly(vinylidene fluoride) (PVDF) film was surface modified by dip coating in an aqueous solution of dopamine on the basis of its self-polymerization and strong adhesion feature. The self-polymerization and deposition rates of dopamine on film surfaces increased with increasing temperature as evaluated by both spectroscopic ellipsometry and scanning electronic microscopy (SEM). Changes in the surface morphologies of pDA-coated films as well as the size and shape of pDA particles in the solution were also investigated by SEM, atomic force microscopy (AFM), and transmission electron microscopy (TEM). The surface roughness and surface free energy of pDA-modified films were mainly affected by the reaction temperature and showed only a slight dependence on the reaction time and concentration of the dopamine solution. Additionally, three other typical hydrophobic polymer films of polytetrafluoroethylene (PTFE), poly(ethylene terephthalate) (PET), and polyimide (PI) were also modified by the same procedure. The lyophilicity (liquid affinity) and surface free energy of these polymer films were enhanced significantly after being coated with pDA, as were those of PVDF films. It is indicated that the deposition behavior of pDA is not strongly dependent on the nature of the substrates. This information provides us with not only a better understanding of biologically inspired surface chemistry for pDA coatings but also effective strategies for exploiting the properties of dopamine to create novel functional polymer materials.© 2011 American Chemical Society

Low-pressure electroneutral loose nanofiltration (NF) membranes were facilely fabricated by co-deposition of polyphenol-inspired epigallocatechin gallate (EGCg) and polyethyleneimine (PEI) on polyethersulfone (PES) ultrafiltration substrates. The effects of PEI with different molecular weights on co-deposition behavior, morphologies, surface properties, as well as separation performance of the resultant membranes were investigated in detail. The results showed that with the increase of PEI molecular weight from 600 to 10,000, the co-deposition amount of EGCg/PEI on membrane surface decreased, while the EGCg/PEI selective layer became denser. As a result, the EGCg/PEI 600 co-deposited membrane, which possessed an electroneutral surface with the best hydrophilicity, exhibited the optimal separation performance among the co-deposited membranes in the context of textile wastewater treatment. It had the highest pure water permeability (19.0 L/(m(2).h.bar)) and excellent rejections towards dyes with different charges (e.g. 99.0% for Congo Red) as well as the lowest rejections towards divalent salts (e.g. 4.1% for Na2SO4) at an operating pressure of 2 bar. Moreover, the membranes exhibited good organic solvent resistance, structural stability together with favorable performance in dealing with textile effluent, demonstrating their great potential in practical applications.

We report a straightforward and reproducible electrochemical approach to develop polydopamine-ethanolamine (ePDA-ETA) films to be used as immunosensing interfaces. ETA is strongly attached to polydopamine films during the potentiodynamic electropolymerization of dopamine. The great advantage of the electrochemical methods is to generate the oxidized species (quinones), which can readily react with ETA amine groups present in solution, with the subsequent incorporation of this molecule in the polymer. The presence of ETA and its effect on the electrosynthesis of polydopamine was accessed by cyclic voltammetry, ellipsometry, atomic force microscopy, FTIR and X-ray photoelectron spectroscopy. The adhesive and biocompatible films enable a facile protein linkage, are resilient to flow assays, and display intrinsic anti-fouling properties to block non-specific protein interactions, as monitored by real-time surface plasmon resonance, and confirmed by ellipsometry. Immunoglobulin G (IgG) and Anti-IgG were used in this work as model proteins for the affinity sensor. By using the one-step methodology (ePDA-ETA), the lower amount of immobilized biorecognition element, IgG, compared to that deposited on ePDA or on ETA post-modified film (ePDA/ETA), allied to the presence of ETA, improved the antibody-antigen affinity interaction. The great potential of the developed platform is its versatility to be used with any target biorecognition molecules, allowing both optical and electrochemical detection.