Staff Publications

Staff Publications

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    'Staff publications' is the digital repository of Wageningen University & Research

    'Staff publications' contains references to publications authored by Wageningen University staff from 1976 onward.

    Publications authored by the staff of the Research Institutes are available from 1995 onwards.

    Full text documents are added when available. The database is updated daily and currently holds about 240,000 items, of which 72,000 in open access.

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    CD-MUSIC-EDL modeling of Pb2+ adsorption on birnessites : Role of vacant and edge sites
    Zhao, Wei ; Tan, Wenfeng ; Wang, Mingxia ; Xiong, Juan ; Liu, Fan ; Weng, Liping ; Koopal, Luuk K. - \ 2018
    Environmental Science and Technology 52 (2018)18. - ISSN 0013-936X - p. 10522 - 10531.
    adsorption - Birnessite - CD-MUSIC Modeling - Electrical double layer model - External surface - Interlayer space - Manganese oxide - Mn average oxidation state - Pb - Rietveld refinement

    The surface complexation modeling of metal adsorption to birnessites is in its infancy compared to the charge-distribution multi-site ion complexation (CD-MUSIC) models for iron/aluminum (hydr)oxides. Therefore, using X-ray diffraction with Rietveld refinement to obtain the reactive sites and their densities, a CD-MUSIC model combined with a Stern-Gouy-Chapman electrical double layer (EDL) model for the external surface and a Donnan model for the interlayer surface is developed for birnessites with different Mn average oxidation state (MnAOS). Proton affinity constants and the charge distributions of Pb surface complexes were calculated a priory. By fitting Pb adsorption data to the model the obtained equilibrium constants (logKPb) of Pb complexes were 6.9-10.9 for the double-corner-sharing and double-edge-sharing Pb2+ complexes on the edge sites and 2.2-6.5 for the triple-corner-sharing Pb2+ complex on the vacancies. The larger logKPb value was obtained for higher MnAOS. Speciation calculations showed that with increasing MnAOS from 3.67 to 3.92 the interlayer surface contribution to the total Pb2+ adsorption increased from 43.2% to 48.6%, and the vacancy contribution increased from 43.9% to 54.7%. The vacancy contribution from interlayer surface was predominant. The present CD-MUSIC-EDL model contributes to understand better the difference in metal adsorption mechanism between birnessite and iron/aluminum (hydr)oxides.

    Microfluidic methods to study emulsion formation
    Muijlwijk, Kelly - \ 2017
    Wageningen University. Promotor(en): C.G.P.H. Schroën, co-promotor(en): C.C. Berton-Carabin. - Wageningen : Wageningen University - ISBN 9789463430715 - 169
    emulsions - microfluidics - food emulsions - droplets - adsorption - colloidal properties - emulsies - microfluidics - voedselemulsies - druppels - adsorptie - colloïdale eigenschappen

    Emulsions are dispersions of one liquid in another that are commonly used in various products, and methods such as high-pressure homogenisers and colloid mills are used to form emulsions. The size and size distribution of emulsion droplets are important for the final product properties and thus need to be controlled. Rapid coalescence of droplets during emulsification increases droplet size and widens the size distribution, and therefore needs to be prevented.

    To increase stability of emulsions, emulsifiers are added to adsorb at the oil-water interface before droplets collide. The time allowed for emulsifier adsorption is typically in the range of sub-milliseconds to seconds and to optimise emulsification processes, emulsifier adsorption and coalescence stability need to be measured in this time-scale, for which the microfluidic methods described in this thesis were developed.

    Chapter 2 provides an overview of existing literature on cross-flow microfluidic emulsification. The effects of various parameters such as microfluidic design, shear forces, and interfacial tension forces on droplet formation and the resulting droplet size are discussed, as well as the use of microfluidics to produce food-grade emulsions. Based on this evaluation, the methods to elucidate interfacial tension and coalescence stability are chosen, and these are presented in the next chapters.

    To measure emulsifier adsorption in the sub-millisecond time-scale, a tensiometric method was developed using a cross-flow microfluidic Y-junction, which is described in Chapter 3. This method is based on the relation between droplet size and interfacial tension at the moment of droplet formation, which is referred to as the acting interfacial tension. The acting interfacial tension of a system with hexadecane as the dispersed phase and sodium dodecylsulfate (SDS, a model surfactant) solutions as the continuous phase was successfully measured for droplet formation times ranging from 0.4 to 9.4 milliseconds and with high expansion rates (100-2000 s-1). Comparison of these results with data from a drop tensiometer (a conventional, static, and supra-second time-scale method) indicates that mass transport in the microfluidic Y-junction is fast and probably not limited by diffusion.

    Emulsifier mass transport conditions were further investigated in Chapter 4. The continuous phase viscosity and velocity were systematically varied and the effect on the acting interfacial tension in presence of water-soluble SDS was measured. We found that the acting interfacial tension was independent of the continuous phase viscosity, but was inversely dependent on continuous phase velocity. Both aspects led us to conclude that convective emulsifier transport in the continuous phase determines the acting interfacial tension in the Y-junction. When using oil-soluble surfactant Span 20 (dissolved in hexadecane), the acting interfacial tension also decreased with increasing continuous phase velocity, and we therefore concluded that convection also dominated mass transport of emulsifiers dissolved in the to-be-dispersed phase.

    The Y-junction method was used in Chapter 5 to elucidate the effect of the dispersed phase viscosity on adsorption of the food-grade emulsifiers Tween 20 (dissolved in the continuous water phase) and Span 20 (dissolved in the dispersed oil phase). A reduction in dispersed phase viscosity sped up adsorption of Tween 20, probably because the shorter hydrocarbon made intercalation of the hydrophobic surfactant tail at the interface easier. Dispersed phase viscosity had an even greater effect on adsorption of Span 20 because convective transport towards the interface was increased.

    Next to interfacial tension, also coalescence can be measured with microfluidics and a microfluidic collision channel was used in Chapter 6 to measure emulsion coalescence stability shortly after droplet formation under flow. Coalescence of emulsions stabilised with proteins was measured at various concentrations, pH values, and adsorption times. We found that protein concentrations just below the concentration needed for monolayer surface coverage may be used effectively. β-lactoglobulin-stabilised emulsions were most stable. Emulsions stabilised with whey protein isolate (with as main component β-lactoglobulin), were less stable and when these proteins were oxidised, this led to reduced stability, therewith indicating that also the oxidative state of proteins needs to be considered in emulsion formulation.

    The relevance of our work for microfluidic research and industrial emulsification processes is discussed in Chapter 7. Microfluidic devices can be used to study emulsion formation and stability under conditions relevant to industrial emulsification processes; at short time-scales and with convective mass transport. In this thesis we used various food-grade ingredients, and with that application in that field has come closer. We expect that the findings on emulsions can also be applied on foams. With the discussed microfluidic devices different aspects that are important for emulsion formation can be decoupled: for example interfacial tension during droplet formation and emulsion coalescence stability. Furthermore, microfluidic methods are available to for example gain insight in emulsion interface mobility and emulsion storage stability, and we envision that all these microfluidic methods will lead to faster ingredient screening, lower ingredient usage, and more energy efficient emulsion production.

    Core-shell particles at fluid interfaces : performance as interfacial stabilizers
    Buchcic, C. - \ 2016
    Wageningen University. Promotor(en): Martien Cohen Stuart, co-promotor(en): R.H. Tromp; Marcel Meinders. - Wageningen : Wageningen University - ISBN 9789462578968 - 140
    stabilization - stabilizers - particles - colloidal properties - adsorption - interface - fluids - stabilisatie - stabiliseermiddelen - deeltjes - colloïdale eigenschappen - adsorptie - grensvlak - vloeistoffen (fluids)

    There is a growing interest in the use of particles as stabilizers for foams and emulsions. Applying hard particles for stabilization of fluid interface is referred to as Pickering stabilization. By using hard particles instead of surfactants and polymers, fluid interfaces can be effectively stabilized against Ostwald ripening and coalescence. A drawback of the use of hard particles as interfacial stabilizers is that they often experience a pronounced energy barrier for interfacial adsorption and that hard particles are very specific with regard to the type of fluid interface they can adsorb to. Soft particles, on the other hand, are known as good stabilizers against coalescence and they spontaneously adsorb to a variety of different fluid interfaces.

    The aim of this thesis was to investigate core-shell particles comprising a hard core and soft shell with regard to their interfacial behaviour and their ability to act as sole stabilizers for foams and emulsions. We hypothesised that the presence of the soft shell allows for easier interfacial adsorption of core-shell particles compared to the hard core particles only. To test this hypothesis, we prepared core-shell particles comprising a solid polystyrene (PS) core and a soft poly-N-isopropylacrylamide (PNIPAM) shell. To ascertain the effect of shell thickness, we prepared a range of core-shell particles with different shell thicknesses, containing identical core particles. We found that core-shell particles are intrinsically surface active and can generate high surface pressures at the air-water interface and oil-water interfaces, whereas core particles seemed to experience a large energy barrier for interfacial adsorption and did not lower the surface tension. We also confirmed by microscopy that core-shell particles are actually adsorbing to the fluid interface and form densely packed interfacial layers. Further, we found that a certain critical thickness of the soft shell is necessary in order to ensure facile interfacial adsorption. If the PNIPAM shell on top of the core particles is well above 100nm thick, particle adsorption at the air-water interface was found to be diffusion limited.

    By gentle hand-shaking we were able to produce dispersion of air bubbles and emulsion droplets solely stabilized by core-shell particles. The resulting bubbles still underwent Ostwald ripening, albeit slowly. For oil-in-water emulsions of hexane and toluene, both of which have a relatively high solubility in the continuous phase, we found that core-shell particles can stop Ostwald ripening. The resulting emulsion droplets adopted pronounced non-spherical shapes, indicating a high elasticity of the interface. The high stability and the remarkable non-spherical shape of the emulsion droplets stabilized by core-shell particles were features we also observed for fluid dispersion stabilized by hard particles. This shows that in terms of emulsion stability core-shell particles behave similar to hard particles as interfacial stabilizer.

    As to why the differences between the stability of bubble and oil dispersions arise could not be finally answered. Yet, microscopic analysis of the interfacial configuration of core-shell particles at the air-water interface reveals some peculiar insights which may suggest that core-shell particles adsorb in a polymer-like fashion with the soft PNIPAM shells adsorbing to the air-water interface only, while the hard PS cores reside in the continuous phase.

    In summary, we showed that core-shell particles with a hard core and a soft shell can indeed combine the advantageous properties of hard and soft particles. The soft shell enables spontaneous adsorption to a variety of fluid interfaces. Despite their spontaneous adsorption, core-shell particles strongly anchor and do not spontaneously desorb from the fluid interface again. Further, the hard core provides enough rigidity to the core-shell particles to allow the establishment of a stress bearing interfacial particle network. This network eventually stops Ostwald ripening in oil-in-water emulsions. Our results therefore show that in the case of oil-water interfaces, core-shell particles can perform better than solely hard particles as interfacial stabilizers.

    Assembly of jammed colloidal shells onto micron-sized bubbles by ultrasound
    Buchcic, C. ; Tromp, R.H. ; Meinders, M.B.J. ; Cohen Stuart, M.A. - \ 2015
    Soft Matter 11 (2015)7. - ISSN 1744-683X - p. 1326 - 1334.
    interfacial rheological properties - aqueous foams - stabilized emulsions - contact-angle - particles - water - surfactants - polymerization - nanoparticles - adsorption
    Stabilization of gas bubbles in water by applying solid particles is a promising technique to ensure long-term stability of the dispersion against coarsening. However, the production of large quantities of particle stabilized bubbles is challenging. The delivery of particles to the interface must occur rapidly compared to the typical time scale of coarsening during production. Furthermore, the production route must be able to overcome the energy barriers for interfacial adsorption of particles. Here we demonstrate that ultrasound can be applied to agitate a colloidal dispersion and supply sufficient energy to ensure particle adsorption onto the air–water interface. With this technique we are able to produce micron-sized bubbles, solely stabilized by particles. The interface of these bubbles is characterized by a colloidal shell, a monolayer of particles which adopt a hexagonal packing. The particles are anchored to the interface owing to partial wetting and experience lateral compression due to bubble shrinkage. The combination of both effects stops coarsening once the interface is jammed with particles. As a result, stable bubbles are formed. Individual particles can desorb from the interface upon surfactant addition, though. The latter fact confirms that the particle shell is not covalently linked due to thermal sintering, but is solely held together by capillary interaction. In summary, we show that our ultrasound approach allows for the straightforward creation of micron-sized particle stabilized bubbles with high stability towards coarsening.
    Comparing foam and interfacial properties of similarly charged protein–surfactant mixtures
    Lech, F.J. ; Meinders, M.B.J. ; Wierenga, P.A. ; Gruppen, H. - \ 2015
    Colloids and Surfaces. A: Physicochemical and Engineering Aspects 473 (2015). - ISSN 0927-7757 - p. 18 - 23.
    sodium dodecyl-sulfate - bovine serum-albumin - air-water interfaces - beta-lactoglobulin - titration calorimetry - binding - sds - adsorption - rheology - layers
    The foam stability of protein–surfactant mixtures strongly depends on the charge of the protein and the surfactant, as well as on their mixing ratio. Depending on the conditions, the mixtures will contain free proteins, free surfactants and/or protein–surfactant complexes. To be able to compare different protein–surfactant mixtures, generic knowledge about the occurrence of each of these states and their relative contribution to foam stability is essential. In this work, the foam stability and interfacial properties of bovine serum albumin (BSA) mixed with sodium dodecyl sulphate (SDS) as well the binding of SDS to BSA as are studied at different molar ratios (MR). A comparison is made with ß-lactoglobulin (BLG) mixed with SDS. Both proteins and SDS are negatively charged at pH 7. The foam stability in the presence of small amounts (up to MR 1) of SDS is half the value of the pure protein solutions. The foam stability for both protein surfactant mixtures reaches a minimum at MR 20. A further increase of the MR leads to an increase of foam stability. The foam stability of BLG–SDS at MR >20 follows the foam stability of pure SDS solutions at equivalent concentrations, while BSA–SDS mixtures have an offset and begin to increase from MR >50. This behaviour was also reflected in the surface pressure and complex dilatational elastic moduli, and could be linked to the binding of the surfactant to the proteins. Both proteins bind SDS at high and low affinity binding sites. BSA's high affinity binding sites have a binding stoichiometry of 5.5 molSDS/molprotein, and BLG's high affinity binding site has a stoichiometry of 0.8 molSDS/molprotein (determined by isothermal titration calorimetry). Binding to the low affinity binding sites, occurs with a binding ratio, leading to an accumulation of free surfactants. While the basic mechanisms underlying the foam properties of mixed systems are not explained in detail by this approach, the foam stability plots of both protein surfactant mixtures could be superimposed using the concentration of free SDS.
    Transformation by photolysis in water in the pesticide model TOXSWA : implementation report
    Beltman, W.H.J. ; Mulder, H.M. ; Horst, M.M.S. ter; Wipfler, E.L. - \ 2015
    Wageningen : Alterra (Alterra report 2649) - 47
    waterverontreiniging - pesticiden - fotolyse - biochemische omzettingen - waterbodems - adsorptie - ecotoxicologie - modellen - water pollution - pesticides - photolysis - biochemical pathways - water bottoms - adsorption - ecotoxicology - models
    The TOXSWA model has been extended with the functionality to simulate photolysis in water. TOXSWA simulates the fate of substances in water bodies to calculate exposure concentrations for aquatic organisms or sediment-dwelling organisms as part of the risk assessment of plant protection products (PPP). Photolysis is modelled as a first-order process, where transformation occurs in the water phase only. The transformation rate is considered to be linearly proportional to global radiation. Studies in outdoor surface water systems can in principle be used to derive the PPP transformation rates due to photolysis.
    Phosphorus leaching from soils: process description, risk assessment and mitigation
    Schoumans, O.F. - \ 2015
    Wageningen : Alterra, Wageningen-UR (Alterra scientific contributions 46) - ISBN 9789462573666 - 261
    nutrient leaching - leaching - soil chemistry - adsorption - phosphorus - phosphate leaching - risk assessment - water quality - eutrophication - nutriëntenuitspoeling - uitspoelen - bodemchemie - adsorptie - fosfor - fosfaatuitspoeling - risicoschatting - waterkwaliteit - eutrofiëring
    Theory of brushes formed by psi-shaped macromolecules at solid-liquid interfaces
    Zhulina, E.B. ; Leermakers, F.A.M. ; Borisov, O.V. - \ 2015
    Langmuir 31 (2015)23. - ISSN 0743-7463 - p. 6514 - 6522.
    starlike polymer brushes - dendronized polymers - gold nanoparticles - good solvent - surface - polysaccharides - adsorption - dendrimers - coatings
    We present a theoretical analysis targeted to describe the structural properties of brushes formed by ¿-shaped macromolecules tethered by terminal segment of stem to planar surface while exposing multiple free branches to the surrounding solution. We use an analytical self-consistent field approach based on the strong stretching approximation, and the assumption of Gaussian elasticity for linear chain fragments of the tethered macromolecules. The effect of weak and strong polydispersity of branches is analyzed. In the case of weakly polydisperse macromolecules, variations in length of branches lead to a more uniform polymer density distribution with slight increase in the brush thickness compared to the case of monodisperse chains with the same degree of polymerization. We demonstrate that in contrast to linear chains, strong polydispersity of ¿-shaped macromolecules does not necessarily lead to strong perturbations in polymer density distribution. In particular, mixed brushes of the so-called “mirror” dendrons (in which number of stem monomers in one component coincides with number of monomers in a branch of the other component, and vice versa) give rise to a unified polymer density distribution with shape independent of the brush composition. The predictions of analytical theory are systematically compared to the results of numerical self-consistent field modeling based on the Scheutjens–Fleer approach
    Interactions between nodes in a physical gel network of telechelic polymers; self-consistent field calculations beyond the cell model
    Bergsma, J.P. ; Leermakers, F.A.M. ; Gucht, J. van der - \ 2015
    Physical Chemistry Chemical Physics 17 (2015)14. - ISSN 1463-9076 - p. 9001 - 9014.
    aqueous-solutions - statistical thermodynamics - chain molecules - adsorption - micelles - formulation - copolymers - scattering - neutron - layer
    Triblock copolymers, with associative end-groups and a soluble middle block, form flower-like micelles in dilute solutions and a physical gel at higher concentrations. In a gel the middle blocks form bridges between domains/nodes that contain the ends. We combine the self-consistent field theory with a simple molecular model to evaluate the pair potential between the nodes. In this model the end-groups are forced to remain in nodes and the soluble middle blocks are in solution. When the distance between the centres of the nodes is approximately the corona diameter, loops can transform into bridges, and the pair potential is attractive. Due to steric hindrance, the interaction is repulsive at smaller distances. Till now a cell-model has been used wherein a central node interacts through reflecting boundary conditions with its images in a spherical geometry. This artificial approach to estimate pair potentials is here complemented by more realistic three-gradient SCF models. We consider the pair interactions for (i) two isolated nodes, (ii) nodes positioned on a line (iii) a central node surrounded by its neighbours in simple cubic ordering, and (iv) a central node in a face centred cubic configuration of its neighbours. Qualitatively, the cell model is in line with the more refined models, but quantitative differences are significant. We also notice qualitative differences for the pair potentials in the specified geometries, which we interpret as a breakdown of the pairwise additivity of the pair potential. This implies that for course grained Monte Carlo or molecular dynamics simulations the best choice for the pair potentials depends on the expected node density.
    Leaching of plant protection products and their transformation products : proposals for improving the assessment of leaching to groundwater in the Netherlands : version 2
    Boesten, J.J.T.I. ; Linden, A.M.A. van der; Beltman, W.H.J. ; Pol, J.W. - \ 2015
    Wageningen : Alterra, Wageningen-UR (Alterra report 2630) - 105
    bodemchemie - adsorptie - pesticiden - uitspoelen - chemische afbraak - schatting - modellen - soil chemistry - adsorption - pesticides - leaching - chemical degradation - estimation - models
    Assessment of leaching of plant protection products to groundwater is an important aspect of the environmental risk assessment of these substances. Analysis of available Dutch groundwater monitoring data for these substances triggered a critical review of the current Dutch leaching assessment. As a result, proposals were developed for improving this assessment. These include: (i) a procedure for correcting systematic errors in measured sorption coefficients, (ii) a preliminary procedure for a quality check of Freundlich exponents, (iii) a flow chart for obtaining parameters describing the relationship between the organic-matter/water distribution coefficient, Kom, and the pH for weak acids, (iv) a procedure for obtaining a Kom endpoint from a population of Kom values including lower and upper limits, (v) a procedure for estimating the total amount of substance in soil from a concentration profile (needed for assessment of degradation half-lives from field experiments). This report is an update of the proposals reported in 2011 by the same authors based on testing the feasibility of the proposals to a few dossiers
    A process synthesis approach for isolation of isoflavones from okara
    Jankowiak, L. ; Mendez Sevillano, D. ; Boom, R.M. ; Ottens, M. ; Zondervan, E. ; Goot, A.J. van der - \ 2015
    Industrial & Engineering Chemistry Research 54 (2015)2. - ISSN 0888-5885 - p. 691 - 699.
    driven process synthesis - antioxidant activity - food - adsorption - extraction - separation - products - recovery - integration - components
    Owing to the complexity of food matrices, process synthesis methodologies have not been as widely applied in the food industry as in the chemical industry. Here, we describe the application of a process synthesis methodology to design a system to separate valuable components from a byproduct of the soymilk production. The method yielded a number of potential processing pathways and relevant mechanistic questions, which required experimental input. The combination of considering the overall system on the level of general transformations, heuristics, and additional insights through experiments resulted in a simplified conceptual process design for the separation of isoflavones from okara with a globally more sustainable choice. The holistic approach within process design as an implication of the methodology is discussed.
    Phosphorus leaching from soils: process description, risk assessment and mitigation
    Schoumans, O.F. - \ 2015
    Wageningen University. Promotor(en): Sjoerd van der Zee, co-promotor(en): Wim Chardon. - Wageningen : Wageningen University - ISBN 9789462572997 - 261
    nutriëntenuitspoeling - uitspoelen - bodemchemie - adsorptie - fosfor - fosfaatuitspoeling - risicoschatting - waterkwaliteit - eutrofiëring - nutrient leaching - leaching - soil chemistry - adsorption - phosphorus - phosphate leaching - risk assessment - water quality - eutrophication
    Er zijn succesvolle management strategieën voor P nodig om de waterkwaliteit te verbeteren en daarvoor is allereerst kwantitatieve informatieve nodig over de ruimtelijke verdeling van de fosfaatbelasting van het oppervlaktewater vanuit landbouwgronden. In Nederland is een protocol fosfaatverzadigde gronden ontwikkeld om het potentiële risico van verhoogde fosfaatconcentraties in het bovenste grondwater (op termijn) te voorspellen voor kalkarme zandgronden, omdat in deze gebieden veel intensieve veehouderij voorkomt. Voor deze grondsoort zijn de parameters voor het protocol vastgesteld. Echter, voor de overige grondsoorten is geen informatie verzameld, waardoor er voor Nederland als geheel geen ruimtelijke beeld bestaat van de mate van fosfaatverzadiging en van het potentiële risico van verhoogde fosfaatconcentraties in het bovenste grondwater. Daarnaast is er behoefte aan eenvoudige methoden om het (huidige) actuele risico van de fosfaatbelasting van het oppervlaktewater in kaart te brengen, zodat inzichtelijk gemaakt kan worden welke gebieden nu al substantieel de oppervlaktewaterkwaliteit en de eutrofiestatus beïnvloeden.
    On the edge energy of lipid membranes and the thermodynamic stability of pores
    Pera, H. ; Kleijn, J.M. ; Leermakers, F.A.M. - \ 2015
    Journal of Chemical Physics 142 (2015). - ISSN 0021-9606 - 14 p.
    molecular-dynamics simulations - interacting chain molecules - statistical thermodynamics - bilayer-membranes - phase-transition - cell-membranes - adsorption - model - size - vesicles
    To perform its barrier function, the lipid bilayer membrane requires a robust resistance against pore formation. Using a self-consistent field (SCF) theory and a molecularly detailed model for membranes composed of charged or zwitterionic lipids, it is possible to predict structural, mechanical, and thermodynamical parameters for relevant lipid bilayer membranes. We argue that the edge energy in membranes is a function of the spontaneous lipid monolayer curvature, the mean bending modulus, and the membrane thickness. An analytical Helfrich-like model suggests that most bilayers should have a positive edge energy. This means that there is a natural resistance against pore formation. Edge energies evaluated explicitly in a two-gradient SCF model are consistent with this. Remarkably, the edge energy can become negative for phosphatidylglycerol (e.g., dioleoylphosphoglycerol) bilayers at a sufficiently low ionic strength. Such bilayers become unstable against the formation of pores or the formation of lipid disks. In the weakly curved limit, we study the curvature dependence of the edge energy and evaluate the preferred edge curvature and the edge bending modulus. The latter is always positive, and the former increases with increasing ionic strength. These results point to a small window of ionic strengths for which stable pores can form as too low ionic strengths give rise to lipid disks. Higher order curvature terms are necessary to accurately predict relevant pore sizes in bilayers. The electric double layer overlap across a small pore widens the window of ionic strengths for which pores are stable.
    Partitioning of humic acids between aqueous solution and hydrogel. 3. Microelectrodic dynamic speciation analysis of free and bound humic metal complexes in the gel phase
    Yasadi, K. ; Pinheiro, J.P. ; Zielinska, K. ; Town, R.M. ; Leeuwen, H.P. van - \ 2015
    Langmuir 31 (2015)5. - ISSN 0743-7463 - p. 1737 - 1745.
    dissolved organic-matter - stability-constants - alginate gel - thin-films - adsorption - ions - fluorescence - substances - cells - soil
    The hydrogel/water partitioning of the various species in the cadmium(II)/soil humic acid (HA) system is studied for two types of gel, using in situ microelectrodic voltammetry. Under the conditions of this work, with HA particles of ca. 25 and 125 nm radius, the CdHA complex is shown to be close to nonlabile toward a 12.5 µm radius microelectrode. This implies that its kinetic contribution to Cd2+ reduction at the medium/microelectrode interface is practically negligible. The polyacrylamide (PAAm) gels equilibrate with the aqueous medium under significant sorption of HA at the gel backbone/gel medium interface, which in turn leads to induced sorption of Cd(II) in the form of immobilized gel-bound CdHA. The rather high total Cd content of the PAAm gel suggests that the binding of Cd2+ by the hydrophobically gel-bound HA is stronger than that for dispersed HA particles. Still, the intraparticulate speciation of Cd(II) over Cd2+ and CdHA corresponds to an intrinsic stability constant similar to that for simple monocarboxylate ligands such as acetate. Alginate gels are negatively charged, and their free [Cdaq2+] is higher than that in the medium by the corresponding Donnan coefficient. On top of that, Cd2+ is specifically sorbed by the gel backbone/gel medium interface to reach accumulation factors as high as a few tens. HA and CdHA accumulate in the outer 20 µm film of gel at the gel/water interface of both gels, but they do not penetrate into the bulk of the alginate gel. Overall, the gel/water interface dictates drastic changes in the speciation of Cd/HA as compared to the aqueous medium, with distinct features for each individual type of gel. The results have broad significance, for example, for predictions of reactivity and bioavailability of metal species which inherently involve partitioning and diffusion into diverse gel layers such as biointerfacial cell walls, biofilm matrices, and mucous membranes.
    Afvangen van fosfaat uit bloembollensector met ijzerzand : Test van maatregelen die fosforemissie verminderen
    Chardon, W.J. ; Groenenberg, J.E. ; Jansen, S. ; Buijert, A. ; Talens, R. ; Krol, A.F. - \ 2014
    Bodem 24 (2014)6. - ISSN 0925-1650 - p. 20 - 22.
    vollegrondsteelt - bloembollen - bodemchemie - emissiereductie - fosfaten - adsorptie - ijzer - bollenstreek - outdoor cropping - ornamental bulbs - soil chemistry - emission reduction - phosphates - adsorption - iron - bollenstreek
    In het oppervlaktewater van de Bollenstreek is de fosfaatconcentratie veel hoger dan de norm van de Europese Kaderrichtlijn Water. Met ijzerzand, een nevenproduct van drinkwaterproductie, kan fosfaat worden afgevangen. Het hoogheemraadschap van Rijnland heeft drie maatregelen op basis van ijzerzand laten onderzoeken op hun effectiviteit. Welke was de beste?
    One-step synthesis of delta-MnO2 nanoparticles using ascorbic acid and their scavenging properties to Pb(II), Zn(II) and methylene blue
    Wang, M.X. ; Pang, P. ; Koopal, L.K. ; Qiu, G.H. ; Wang, Y. ; Liu, F. - \ 2014
    Materials Chemistry and Physics 148 (2014)3. - ISSN 0254-0584 - p. 1149 - 1156.
    high-temperature decomposition - manganese oxide - structural evolution - oxidation-state - layered mno2 - birnessite - adsorption - mechanism - nanobelts - dissolution
    To obtain delta-MnO2 particles with a large specific surface area, MnO2 was synthesized in an ice-water bath using ascorbic acid (AA) to reduce KMnO4. At pH 3 and 5 and KMnO4/AA molar ratios of 8/1 and 10/1, nanoparticles of delta-MnO2 were produced. The specific surface areas (SSAs) of the samples ranged from 163 to 207 m(2)/g. The Mn average oxidation state of the samples ranged from 3.88 to 3.98 and increased with the KMnO4/AA ratio and pH. The adsorption of the samples with respect to metal ion revealed pseudo adsorption capacities of 3425 mmol Pb2+/kg and 1789 mmol Zn2+/kg. The decolorization behaviors of sample S10-5 (produced at pH 5 and KMnO4/AA molar ratios of 10/1) to methylene blue (MB) were compared at different pH values and temperatures. After 120 min at room temperature, 97% of the MB was adsorbed, and approximately 68% was oxidized. The adsorbed amount and the level of oxidation increased with increasing temperature and decreased with increasing pH. (C) 2014 Elsevier B.V. All rights reserved.
    Direct observation of ionic structure at solid-liquid interfaces: A deep look into the Stern layer
    Siretanu, I. ; Ebeling, D. ; Andersson, M.P. ; Stipp, S.L.S. ; Philipse, A. ; Cohen Stuart, M.A. ; Ende, D. van den; Mugele, F. - \ 2014
    Scientific Reports 4 (2014). - ISSN 2045-2322 - 7 p.
    molecular-dynamics - charging behavior - atomic-resolution - surface-charge - gibbsite - adsorption - water - (hydr)oxides - force - kaolinite
    The distribution of ions and charge at solid-water interfaces plays an essential role in a wide range of processes in biology, geology and technology. While theoretical models of the solid-electrolyte interface date back to the early 20th century, a detailed picture of the structure of the electric double layer has remained elusive, largely because of experimental techniques have not allowed direct observation of the behaviour of ions, i.e. with subnanometer resolution. We have made use of recent advances in high-resolution Atomic Force Microscopy to reveal, with atomic level precision, the ordered adsorption of the mono- and divalent ions that are common in natural environments to heterogeneous gibbsite/silica surfaces in contact with aqueous electrolytes. Complemented by density functional theory, our experiments produce a detailed picture of the formation of surface phases by templated adsorption of cations, anions and water, stabilized by hydrogen bonding.
    Mesoscale models of dispersions stabilized by surfactants and colloids
    Sman, R.G.M. van der; Meinders, M.B.J. - \ 2014
    Advances in Colloid and Interface Science 211 (2014). - ISSN 0001-8686 - p. 63 - 76.
    dissipative particle dynamics - fluid-fluid interfaces - lattice-boltzmann simulations - phase-separation dynamics - pickering emulsions - soluble surfactants - amphiphilic fluids - binary fluids - adsorption - flows
    In this paper we discuss and give an outlook on numerical models describing dispersions, stabilized by surfactants and colloidal particles. Examples of these dispersions are foams and emulsions. In particular, we focus on the potential of the diffuse interface models based on a free energy approach, which describe dispersions with the surface-active agent soluble in one of the bulk phases. The free energy approach renders thermodynamic consistent models with realistic sorption isotherms and adsorption kinetics. The free energy approach is attractive because of its ability to describe highly complex dispersions, such as emulsions stabilized by ionic surfactants, or surfactant mixtures and dispersions with surfactant micelles. We have classified existing numerical methods into classes, using either a Eulerian or a Lagrangian representation for fluid and for the surfactant/colloid. A Eulerian representation gives a more coarse-grained, mean field description of the surface-active agent, while a Lagrangian representation can deal with steric effects and larger complexity concerning geometry and (amphiphilic) wetting properties of colloids and surfactants. However, the similarity between the description of wetting properties of both Eulerian and Lagrangian models allows for the development of hybrid Eulerian/Lagrangian models having advantages of both representations.
    Influence of the relative humidity on the morphology of inkjet printed spots of IgG on a non-porous substrate.
    Mujawar, L.H. ; Kuerten, J.G.M. ; Siregar, D.P. ; Amerongen, A. van; Norde, W. - \ 2014
    RSC Advances : An international journal to further the chemical sciences 4 (2014)37. - ISSN 2046-2069 - p. 19380 - 19388.
    experimental-verification - protein microarrays - dna microarrays - contact-angle - evaporation - surfaces - drops - performance - fabrication - adsorption
    During the drying of inkjet printed droplets, the solute particles (IgG-Alexa-635 molecules) in the drop may distribute unevenly on the substrate, resulting in a “coffee-stain” spot morphology. In our study, we investigated the influence of the relative humidity on the distribution of inkjet printed fluorophore labeled IgG molecules on a polystyrene substrate. A theoretical model for an evaporating droplet was developed in order to predict the changes in the spot diameter, height and volume of a drying droplet. An experiment was performed where a sessile droplet was monitored using a CCD camera installed on a goniometer and good agreement was found between the experimental results and simulation data. We also compared the predicted morphology for an inkjet-printed microarray spot with the experimental results where IgG molecules were printed for various relative humidities. The spot morphology of the dried spots was analyzed by a confocal laser microscopy. At a lower relative humidity (i.e.,
    Catalytic Deoxygenation of Fatty Acids: Elucidation of the Inhibition Process
    Hollak, S.A.W. ; Jong, K.P. de; Es, D.S. van - \ 2014
    ChemCatChem 6 (2014)9. - ISSN 1867-3880 - p. 2648 - 2655.
    stearic-acid - mesoporous carbon - vegetable-oils - diesel fuel - continuous decarboxylation - palladium catalysts - reaction pathways - supported nickel - hydrocarbons - adsorption
    Catalytic deoxygenation of unsaturated fatty acids in the absence of H2 is known to suffer from significant catalyst inhibition. Thus far, no conclusive results have been reported on the cause of deactivation. Here we show that CC double bonds present in the feed or the products dramatically reduce the deoxygenation activity of supported palladium catalysts. In the case of stearic acid deoxygenation the addition of 0.1 equivalents of a mono-unsaturated fatty acid or olefin already reduces the catalytic deoxygenation activity by 60¿%. This effect becomes more pronounced with an increasing number of double bonds. The inhibition is shown to be reversible in H2 atmosphere, indicating no significant contribution from irreversibly deposited hard coke. Furthermore, the type of support material has no apparent effect on catalyst inhibition. Hence we propose that initial catalyst inhibition proceeds through reversible adsorption of CC double bonds on the palladium active sites.
    Improved emulsion stability by succinylation of patatin is caused by partial unfolding rather than charge effects
    Delahaije, R.J.B.M. ; Wierenga, P.A. ; Giuseppin, M.L.F. ; Gruppen, H. - \ 2014
    Journal of Colloid and Interface Science 430 (2014). - ISSN 0021-9797 - p. 69 - 77.
    in-water emulsions - protein-exposed hydrophobicity - beta-lactoglobulin - drop size - adsorption - flocculation - interface - stabilization - ph - dependence
    This study investigates the influence of succinylation on the molecular properties (i.e. charge, structure and hydrophobicity) and the flocculation behavior of patatin-stabilized oil-in-water emulsions. Patatin was succinylated to five degrees (0% (R0) to 57% (R2.5)). Succinylation not only resulted in a change of the protein charge but also in (partial) unfolding of the secondary structure, and consequently in an increased initial adsorption rate of the protein to the oil–water interface. The stability against salt-induced flocculation showed two distinct regimes, instead of a gradual shift in stability as expected by the DLVO theory. While flocculation was observed at ionic strengths > 30 mM for the emulsions stabilized by the variants with the lowest degrees of modification (R0–R1), the other variants (R1.5–R2.5) were stable against flocculation ¿ 200 mM. This was related to the increased initial adsorption rate, and the consequent transition from a protein-poor to a protein-rich regime. This was confirmed by the addition of excess protein to the emulsions stabilized by R0–R1 which resulted in stability against salt-induced flocculation. Therefore, succinylation of patatin indirectly results in stability against salt-induced flocculation, by increasing the initial adsorption rate of the protein to the oil–water interface, leading to a shift to the protein-rich regime.
    Partitioning of humic acids between aqueous solution and hydrogel: Concentration profiling of humic acids in hydrogel phases.
    Zielinska, K. ; Town, R.M. ; Yasadi, K. ; Leeuwen, H.P. van - \ 2014
    Langmuir 30 (2014)8. - ISSN 0743-7463 - p. 2084 - 2092.
    natural organic-matter - fluorescence correlation spectroscopy - diffusion-coefficients - mineral particles - ionic-strength - alginate gel - fulvic-acid - substances - adsorption - soil
    The partitioning of the natural polyelectrolyte humic acid (HA) from an aqueous dispersion into a model biomimetic gel (alginate) and a synthetic polyacrylamide gel (PAAm) is explored. In both gels, the spatial distribution of HA in the gel body, as measured by confocal laser scanning microscopy, is markedly nonhomogeneous. A striking feature is the enhanced accumulation of HA in a thin film of thickness ca. 15 µm at the surface of the gel body, resulting in average local concentrations that are, for PAAm and alginate respectively, a factor of 10 and 4 greater than that in the bulk solution. The time dependence of accumulation in the surface film is predominantly controlled by the diffusive supply of HA from the aqueous medium, with a time constant on the order of 103 s for both gels. The concentration of HA within the bulk gel body differs significantly from that in the bulk aqueous medium: substantially higher for PAAm but much lower for alginate. The results are significant for understanding the nature and rate of sink/source functioning at permeable phases in contact with aqueous media, e.g., biofilms and gel-like layers at biological interfaces or employed in chemical speciation sensors.
    Solid phase microextraction speciation analysis of triclosan in aqueous mediacontaining sorbing nanoparticles
    Zielinska, K. - \ 2014
    Environmental Chemistry 11 (2014)1. - ISSN 1448-2517 - p. 72 - 76.
    nd-spme - samples - water - adsorption - products - binding - surface
    Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid phase poly(dimethylsiloxane) (PDMS). Furthermore, they appear to aggregate at the PDMS–water interface. The total triclosan concentration in the solid phase thus includes both the free and the NP-bound forms. Proper computation of the analyte concentration in the sample medium requires (i) consideration of the speciation of triclosan inside the solid phase and (ii) elimination of the effects of aggregation of NP complexes at the solid phase–bulk medium interface. Possible solutions include application of a protective membrane with pore size smaller than the NP diameter. This allows measurement of the free triclosan concentration, albeit at the cost of longer accumulation times and loss of kinetic information on the triclosan–NP complex.
    Linking lipid architecture to bilayer structure and mechanics using self-consistent field modelling
    Pera, H. ; Kleijn, J.M. ; Leermakers, F.A.M. - \ 2014
    Journal of Chemical Physics 140 (2014). - ISSN 0021-9606 - 23 p.
    interacting chain molecules - statistical thermodynamics - spontaneous curvature - bending moduli - association colloids - membranes - elasticity - adsorption - monolayers - vesicles
    To understand how lipid architecture determines the lipid bilayer structure and its mechanics, we implement a molecularly detailed model that uses the self-consistent field theory. This numerical model accurately predicts parameters such as Helfrichs mean and Gaussian bending modulus k c and k ¯ and the preferred monolayer curvature J m 0 , and also delivers structural membrane properties like the core thickness, and head group position and orientation. We studied how these mechanical parameters vary with system variations, such as lipid tail length, membrane composition, and those parameters that control the lipid tail and head group solvent quality. For the membrane composition, negatively charged phosphatidylglycerol (PG) or zwitterionic, phosphatidylcholine (PC), and -ethanolamine (PE) lipids were used. In line with experimental findings, we find that the values of k c and the area compression modulus k A are always positive. They respond similarly to parameters that affect the core thickness, but differently to parameters that affect the head group properties. We found that the trends for k ¯ and J m 0 can be rationalised by the concept of Israelachivili's surfactant packing parameter, and that both k ¯ and J m 0 change sign with relevant parameter changes. Although typically k ¯
    Terrestrial selenium distribution in China is potentially linked to monsoonal climate
    Blazina, T. ; Sun, Y. ; Voegelin, A. ; Lenz, M. ; Berg, M. ; Winkel, L.H.E. - \ 2014
    Nature Communications 5 (2014). - ISSN 2041-1723
    red clay formation - loess plateau - atmospheric selenium - trace-metals - adsorption - speciation - pliocene - records - water - soil
    The prevalence of terrestrial environments low in the essential trace element selenium (Se) results in large-scale Se deficiency worldwide. However, the underlying processes leading to Se-depleted environments have remained elusive. Here we show that over the last 6.8 million years (Ma) climatic factors have played a key role in the Se distribution in loess–paleosol sequences in the Chinese Loess Plateau (CLP), which lies in a severely Se-depleted region with a history of Se deficiency-related diseases. We use a combination of geochemical and paleoclimate data to demonstrate that during interglacial periods between 2.30 and 0.16¿Ma, variations in the Se concentration in the CLP are potentially related to variability in Se input via East Asian monsoon-derived precipitation. Our results identify precipitation as an important controlling factor of Se distribution in monsoonal China. We suggest that atmospheric Se inputs via precipitation could also play an important role in other regions worldwide.
    Technologieën voor verwijdering gewasbeschermingsmiddelen
    Beerling, E.A.M. - \ 2014
    gewasbescherming - chemische bestrijding - milieueffect - cost effective analysis - afvalverwerking - oxidatie - scheidingsapparaten - bioremediëring - adsorptie - plant protection - chemical control - environmental impact - cost effectiveness analysis - waste treatment - oxidation - separators - bioremediation - adsorption
    Mogelijk geschikte technieken om chemische gewasbeschermingsmiddelen te verwijderen zodat ze niet het milieu verontreiningen worden geïnventariseerd met behulp van onafhankelijke experts uit de watersector (o.a. KWR, Wetsus, Mannen van de Wit en Stowa)
    Gedrag van chloorprofam en 3-chlooraniline in de bodem : bepaling van adsorptie, omzetting en uitloging met tarragrond van aardappelen
    Beltman, W.H.J. ; Matser, A.M. ; Linden, A.M.A. van der; Brand, E. - \ 2014
    Wageningen : Alterra, Wageningen-UR (Alterra-rapport 2523) - 65
    aardappelopslagplaatsen - aardappelen - opslag - kiemremmers - adsorptie - uitspoelen - grondwaterverontreiniging - potato stores - potatoes - storage - germination inhibitors - adsorption - leaching - groundwater pollution
    Bij de bewaring van aardappelen wordt als kiemremmer de werkzame stof chloorprofam gebruikt. Na verwerking van de aardappelen in de fabriek blijft chloorprofam en haar omzettingsprodukt 3-chlooraniline in de resterende tarragrond aanwezig. De tarragrond wordt hergebruikt in grootschalige bodemtoepassingen. Omzetting, adsorptie en uitloging van chloorprofam en haar metaboliet 3-chlooraniline zijn onderzocht met tarragrond van aardappelen (onbelast en belast met chloorprofam) en met bouwvoorgrond. De omzettingssnelheid van chloorprofam en 3-chlooraniline is bepaald in bouwvoorgrond, in onverzadigde onbelaste tarragrond en in waterverzadigde onbelaste tarragrond. De adsorptieparameters van de Freundlich sorptie isotherm zijn bepaald voor 3-chlooraniline in onbelaste tarragrond en in bouwvoorgrond. De uitloogproeven zijn gedaan met onverzadigde belaste tarragrond en met waterverzadigde belaste tarragrond. De omzettingssnelheden en adsorptieparameters uit deze studie worden gebruikt voor het bepalen van het risico van uitspoeling van chloorprofam en 3-chlooraniline uit grote bodemtoepassingen naar het grondwater.
    Implications of nanoparticles in the aquatic environment
    Velzeboer, I. - \ 2014
    Wageningen University. Promotor(en): Bart Koelmans. - Wageningen : Wageningen University - ISBN 9789461739506 - 253
    microplastics - polychloorbifenylen - nanotechnologie - adsorptie - ecotoxicologie - aquatisch milieu - verontreinigde sedimenten - aquatische ecologie - microplastics - polychlorinated biphenyls - nanotechnology - adsorption - ecotoxicology - aquatic environment - contaminated sediments - aquatic ecology
    De productie en het gebruik van synthetische nanodeeltjes (ENPs) nemen toe en veroorzaken toenemende emissies naar het milieu. Dit proefschrift richt zich op de implicaties van ENPs in het aquatisch milieu, met de nadruk op het sediment, omdat er wordt verwacht dat ENPs hoofdzakelijk in het aquatisch sediment terecht zullen komen. ENPs kunnen directe effecten veroorzaken op organismen in het aquatisch milieu, indirecte effecten op het levensgemeenschap niveau en/of voedselweb en kunnen effecten op het gedrag en de risico’s van andere contaminanten hebben. Om de risico’s van ENPs vast te stellen, is niet alleen informatie nodig over het gevaar, oftewel de kans op een effect, maar ook over de kans op blootstelling.
    Multi-face modeling to predict free zinc ion concentrations in low-zinc soils
    Duffner, A. ; Weng, L. ; Hoffland, E. ; Zee, S.E.A.T.M. van der - \ 2014
    Environmental Science and Technology 48 (2014)10. - ISSN 0013-936X - p. 5700 - 5708.
    donnan membrane technique - organic-matter - heavy-metals - contaminated soils - isotopic exchange - humic substances - trace-metals - sandy soil - adsorption - speciation
    Multi-surface models are widely used to assess the potential ecotoxicological risk in metal-contaminated soils. Their accuracy in predicting metal speciation in soils with low metal levels was not yet tested. Now highly sensitive analytical techniques are available to experimentally validate such models at low concentration levels. The objective of this study was to test the accuracy of a multi-surface model to predict the Zn2+ concentration and to improve our understanding of Zn bioavailability in low-Zn soils. High-Zn soils were included as controls. Model parameters were determined independently on the basis of earlier peer-reviewed publications. Model output was validated against free Zn2+ concentrations determined with the soil column Donnan membrane technique in a range of soils varying in potentially available Zn, organic matter, clay silicate, and iron (hydr)oxide contents and pH. Deviations between predicted Zn2+ concentrations and experimentally determined values over the whole Zn concentration range were less or equal to the experimental standard error, except for one low-Zn soil. The Zn2+ concentration was mainly controlled by adsorption, where organic matter was predicted to be the dominant soil sorbent. The predicted Zn2+ concentration depends more sensitively upon changes of the reactive Zn pool (application of 0.6, 1.2, 2.4, and 3.6 mg of Zn kg–1 of soil) and organic matter content (±0.2 and 0.4%) than pH changes (±0.5 and 1 pH unit).
    Stability of (Bio)Functionalized Porous Aluminum Oxide
    Debrassi, A. ; Ribbera, A. ; Vos, W.M. de; Wennekes, T. ; Zuilhof, H. - \ 2014
    Langmuir 30 (2014). - ISSN 0743-7463 - p. 1311 - 1320.
    self-assembled monolayers - lactic-acid bacteria - lactobacillus-plantarum - nanoporous alumina - click chemistry - anodic alumina - surfaces - adsorption - membrane - carbohydrate
    Porous aluminum oxide (PAO), a nanostructured support for, among others, culturing microorganisms, was chemically modified in order to attach biomolecules that can selectively interact with target bacteria. We present the first comprehensive study of monolayer-modified PAO using conditions that are relevant to microbial growth with a range of functional groups (carboxylic acid, a-hydroxycarboxylic acid, alkyne, alkene, phosphonic acid, and silane). Their stability was initially assessed in phosphate-buffered saline (pH 7.0) at room temperature. The most stable combination (PAO with phosphonic acids) was further studied over a range of physiological pHs (4–8) and temperatures (up to 80 °C). Varying the pH had no significant effect on the stability, but it gradually decreased with increasing temperature. The stability of phosphonic acid-modified PAO surfaces was shown to depend strongly on the other terminal group of the monolayer structure: in general, hydrophilic monolayers were less stable than hydrophobic monolayers. Finally, an alkyne-terminated PAO surface was reacted with an azide-linked mannose derivative. The resulting mannose-presenting PAO surface showed the clearly increased adherence of a mannose-binding bacterium, Lactobacillus plantarum, and also allowed for bacterial outgrowth.
    Strong Sorption of PCBs to Nanoplastics, Microplastics, Carbon Nanotubes, and Fullerenes
    Velzeboer, I. ; Kwadijk, C.J.A.F. ; Koelmans, A.A. - \ 2014
    Environmental Science and Technology 48 (2014)9. - ISSN 0013-936X - p. 4869 - 4876.
    polycyclic aromatic-hydrocarbons - hydrophobic organic-chemicals - polychlorinated biphenyl sorption - mytilus-edulis l. - aquatic sediments - activated carbon - marine-environment - passive samplers - humic acids - adsorption
    The presence of microplastic and carbon-based nanoparticles in the environment may have implications for the fate and effects of traditional hydrophobic chemicals. Here we present parameters for the sorption of 17 CB congeners to 10–180 µm sized polyethylene (micro-PE), 70 nm polystyrene (nano-PS), multiwalled carbon nanotubes (MWCNT), fullerene (C60), and a natural sediment in the environmentally relevant 10–5–10–1 µg L–1 concentration range. Effects of salinity and sediment organic matter fouling were assessed by measuring the isotherms in fresh- and seawater, with and without sediment present. Sorption to the “bulk” sorbents sediment organic matter (OM) and micro-PE occurred through linear hydrophobic partitioning with OM and micro-PE having similar sorption affinity. Sorption to MWCNT and nano-PS was nonlinear. PCB sorption to MWCNT and C60 was 3–4 orders of magnitude stronger than to OM and micro-PE. Sorption to nano-PS was 1–2 orders of magnitude stronger than to micro-PE, which was attributed to the higher aromaticity and surface–volume ratio of nano-PS. Organic matter effects varied among sorbents, with the largest OM fouling effect observed for the high surface sorbents MWCNT and nano-PS. Salinity decreased sorption for sediment and MWCNT but increased sorption for the polymers nano-PS and micro-PE. The exceptionally strong sorption of (planar) PCBs to C60, MWCNT, and nano-PS may imply increased hazards upon membrane transfer of these particles.
    Bifunctional immobilization of a hyperthermostable endo ß 1,3 glucanase
    Przybysz, A. ; Volmer, A.A. ; Westphal, A.H. ; Berkel, W.J.H. van - \ 2014
    Applied Microbiology and Biotechnology 98 (2014)3. - ISSN 0175-7598 - p. 1155 - 1163.
    pyrococcus-furiosus - enzyme immobilization - epoxy supports - proteins - stabilization - adsorption - reagent - acid
    Laminarinase A (LamA) from Pyrococcus furiosus is a hyperthermostable endo-ß-1,3-glucanase (EC belonging to the glycosyl hydrolase family GH16. Here, we report the two-step immobilization of LamA on macroporous acrylic epoxy beads, extra-functionalized with disulfide groups. To facilitate initial immobilization via thiol–disulfide exchange, we introduced, by site-directed mutagenesis, a superficial cysteine residue near the protein C-terminal end. The thus-obtained S296C variant showed similar catalytic properties as native LamA. The activity of immobilized S296C displayed an inverse relationship with particle size. Use of conventional beads (150–300 µm in diameter) obstructed the catalytic efficiency due to pore diffusion limitation of the polysaccharide substrate. Bifunctional attachment to milled beads (20–40 µm) resulted in high enzyme load and outstanding catalytic features. Bifunctional immobilized S296C showed extreme pH stability and could be repeatedly used at 60 °C without significant activity loss.
    Effect of charged polysaccharides on the techno-functional properties of fractions obtained from algae soluble protein isolate
    Schwenzfeier, A. ; Wierenga, P.A. ; Eppink, M.H.M. ; Gruppen, H. - \ 2014
    Food Hydrocolloids 35 (2014). - ISSN 0268-005X - p. 9 - 18.
    in-water emulsions - diffusing wave spectroscopy - tetraselmis sp - adsorption - microalgae - dissociation - hydrolysis - stability
    It has been suggested previously that charged polysaccharides present in algae soluble protein isolate (ASPI) contribute to its foaming and emulsifying properties. In this study ASPI was fractioned into one fraction enriched in uronic acids (the building blocks of charged polysaccharides, [ASPI-UA]), one enriched in protein (ASPI-P) and one containing small, dissociated (glyco-)proteins (ASPI-S). Emulsions prepared using ASPI-UA were stable against flocculation between pH 3e7, while ASPI-P and ASPI-S showed decreased emulsion stabilities around pH 5. This indicates the importance of the charged polysaccharides present in ASPI for emulsion stability at pH 5. For the foaming properties of ASPI no effect of charged polysaccharides was observed. Instead, ASPI-S showed considerably higher foam stabilities at pH 5e7 than the other fractions. These results suggest that dependent on the application charged polysaccharides or dissociated (glyco-) proteins can contribute to ASPI’s techno-functional properties. Its further fractionation yields a fraction with improved emulsion stability and a fraction with improved foaming properties.
    Sulphate reduction and calcite precipitation in relation to internal eutrophication of groundwater fed alkaline fens
    Cirkel, D.G. ; Beek, C.G.E.M. van; Witte, J.P.M. ; Zee, S.E.A.T.M. van der - \ 2014
    Biogeochemistry 117 (2014)2-3. - ISSN 0168-2563 - p. 375 - 393.
    organic-matter - calcareous fens - phosphate - sulfur - soils - water - netherlands - sediments - adsorption - peatland
    Although in Europe atmospheric deposition of sulphur has decreased considerably over the last decades, groundwater pollution by sulphate may still continue due to pyrite oxidation in the soil as a result of excessive fertilisation. Inflowing groundwater rich in sulphate can change biogeochemical cycling in nutrient-poor wetland ecosystems. Incoming sulphate loads may induce internal eutrophication as well as the accumulation of dissolved sulphide, which is phytotoxic. We, however, argue that upwelling sulphate rich groundwater may also promote the conservation of rare and threatened alkaline fens, since excessive fertilisation and pyrite oxidation also produces acidity, which invokes calcite dissolution, and increased alkalinity and hardness (Ca2+ + Mg2+) of the inflowing groundwater. Our observations in a very species-rich wetland nature reserve show that sulphate is reduced and effectively precipitates as iron sulphides when this calcareous and sulphate rich groundwater flows upward through the organic soil of the investigated nature reserve. Furthermore, we show that sulphate reduction coincides with an increase in alkalinity production, which in our case results in active calcite precipitation in the soil. In spite of the occurring sulphate reduction we found no evidence for internal eutrophication. Extremely low phosphorous concentration in the pore water could be attributed to a high C:P ratio of soil organic matter and co-precipitation with calcite. Our study shows that seepage dependent alkaline fen ecosystems can be remarkably resilient to fertilisation and pyrite oxidation induced groundwater quality changes.
    Surface Pressure and Elasticity of Hydrophobin HFBII Layers on the Air-Water Interface: Rheology Versus Structure Detected by AFM Imaging
    Stanimirova, R.D. ; Gurkov, T.D. ; Kralchevsky, P.A. ; Balashev, K.T. ; Stoyanov, S.D. ; Pelan, E.G. - \ 2013
    Langmuir 29 (2013)20. - ISSN 0743-7463 - p. 6053 - 6067.
    class-ii hydrophobins - air/water interface - langmuir monolayers - trichoderma-reesei - proteins - films - adsorption - stability - emulsions - mechanisms
    Here, we combine experiments with Langmuir trough and atomic force microscopy (AFM) to investigate the reasons for the special properties of layers from the protein HFBII hydrophobin spread on the airwater interface. The hydrophobin interfacial layers possess the highest surface dilatational and shear elastic moduli among all investigated proteins. The AFM images show that the spread HFBII layers are rather inhomogeneous, (i.e., they contain voids, monolayer and multilayer domains). A continuous compression of the layer leads to filling the voids and transformation of a part of the monolayer into a trilayer. The trilayer appears in the form of large surface domains, which can be formed by folding and subduction of parts from the initial monolayer. The trilayer appears also in the form of numerous submicrometer spots, which can be obtained by forcing protein molecules out of the monolayer and their self-assembly into adjacent pimples. Such structures are formed because not only the hydrophobic parts, but also the hydrophilic parts of the HFBII molecules can adhere to each other in the water medium. If a hydrophobin layer is subjected to oscillations, its elasticity considerably increases, up to 500 mN/m, which can be explained with compaction. The relaxation of the layers tension after expansion or compression follows the same relatively simple law, which refers to two-dimensional diffusion of protein aggregates within the layer. The characteristic diffusion time after compression is longer than after expansion, which can be explained with the impedence of diffusion in the more compact interfacial layer. The results shed light on the relation between the mesoscopic structure of hydrophobin interfacial layers and their unique mechanical properties that find applications for the production of foams and emulsions of extraordinary stability; for the immobilization of functional molecules at surfaces, and as coating agents for surface modification.
    Sterke vermindering van fosfaatuitspoeling uit landbouwgronden met de fosfaatbindende drain
    Groenenberg, J.E. ; Chardon, W.J. ; Koopmans, G.F. - \ 2013
    draineerbuizen - drainagewater - ijzer - adsorptie - waterkwaliteit - fosfaten - veldproeven - drain pipes - drainage water - iron - adsorption - water quality - phosphates - field tests
    Voor gedraineerde landbouwgronden (meer dan 50% in Nederland) heeft Alterra de fosfaatbindende drain ontwikkeld. Dit is een normale buisdrain die is ingebed in ijzerzand. De omhulling met ijzerzand bindt het fosfaat uit het fosfaatrijke water voor het de drainbuis instroomt. Het schone water wordt afgevoerd naar het oppervlaktewater.
    Surface and mineral structure of ferrihydrite
    Hiemstra, T. - \ 2013
    Geochimica et Cosmochimica Acta 105 (2013). - ISSN 0016-7037 - p. 316 - 325.
    oxide-water interface - x-ray-absorption - nanocrystalline material - synthetic ferrihydrite - mossbauer-spectroscopy - 6-line ferrihydrite - iron oxyhydroxide - model - adsorption - nanoparticles
    Ferrihydrite (Fh) is an yet enigmatic nano Fe(III)-oxide material, omnipresent in nature that can bind ions in large quantities, regulating bioavailability and ion mobility. Although extensively studied, to date no proper view exists on the surface structure and composition, while it is of vital importance to our understanding of ion complexation in terrestrial and aquatic systems. Here, the surface structure of Fh is elucidated in relation to that of the mineral core, showing a unique surface composition differing from the mineral core. The mineral core is basically defect-free for all Fh particles. Key for understanding Fh is the very large contribution of the surface as an “inter-phase”. The surface of Fh is depleted by two specific types of polyhedra (Fe2,Fe3). Surface depletion (SD) explains the observed particle size dependency of the (a) Pair Distribution Function (PDF) derived from High Energy X-ray total Scattering (HEXS), (b) thermogravimetric water content, and (c) mass density. It also explains the isotopic 57Fe exchange ratio. Due to surface groups, two-line Fh particles are water rich but its mineral core is hydrogen poor. The SD model elucidates the surface structure of crystal faces of idealized Fh such as the 1 -1 0 and 1 -1 1 type of faces that may strongly contribute (e.g. ~75 ± 10%) to the total surface area. These faces are terminated by protruding Fe1 octahedra, creating the singly-coordinated FeOH(H) groups at the Fh surface. Alternating rows of Fe1 octahedra with singly-coordinated surface groups enable the formation of either double corner (2C) or edge (1E) surface complexes. For Fh, the site densities derived are much higher than for goethite. In combination with the high surface area, it makes Fh to an extremely reactive natural phase.
    Influence of soil humic and fulvic acid on the activity and stability of lysozyme and urease
    Li, Y. ; Tan, W. ; Koopal, L.K. ; Wang, M. ; Liu, Fan ; Norde, W. - \ 2013
    Environmental Science and Technology 47 (2013). - ISSN 0013-936X - p. 5050 - 5056.
    isothermal titration calorimetry - insecticidal cry1ab protein - ionic-strength - prion protein - ph - adsorption - complexes - binding - substances - fractions
    Humic substances (HS), including humic acids (HA) and fulvic acids (FA), are important components of soil systems. HS form strong complexes with oppositely charged proteins, which will lead to changes in the enzyme activity. The effect of soil HS on the activity and stability of two enzymes was investigated as a function of pH, ionic strength, and mass ratio HS/enzyme. Humic acid (JGHA) and fulvic acid (JGFA) are negatively charged, lysozyme is net positive at pH values below 10.4, and urease is net positive below pH 5.2 or net negative above pH 5.2. The enzyme activities in the HS-enzyme complexes were suppressed when the enzymes were oppositely charged to the HS. The largest activity suppression was observed around the mass ratio HS/enzyme where the HS-protein complex was at its isoelectric point (IEP). At the IEP strong aggregation of the complexes led to encapsulation of the enzyme. The ionic strength was important; an increase decreased complex formation, but increased aggregation. Due to the larger hydrophobicity of JGHA than JGFA, the reduction in enzyme activity was stronger for JGHA. The enzyme stability also decreased maximally at mass ratio around the IEP of the complex when HS and protein were oppositely charged. When urease and HS were both negatively charged no complexes were formed, but the presence of JGHA or JGFA improved the activity and stability of the enzyme.
    Proton binding to soil humic and fulvic acids: Experiments and NICA-Donnan modelling
    Tan, W. ; Xiong, J. ; Li, Y. ; Wang, M. ; Weng, L. ; Koopal, L.K. - \ 2013
    Colloids and Surfaces. A: Physicochemical and Engineering Aspects 436 (2013). - ISSN 0927-7757 - p. 1152 - 1158.
    natural organic-matter - metal-ion binding - potentiometric titrations - affinity distributions - base properties - substances - heterogeneity - parameters - adsorption
    Proton binding to one soil fulvic acid (JGFA), two soil humic acids (JGHA, JLHA) and a lignite-based humic acid (PAHA) was investigated. The results were fitted to NICA-Donnan model and compared directly with the predictions using the generic parameters. NICA-Donnan model can describe proton binding satisfactorily when parameter fitting is allowed for humic substance (HS). However, predictions based on the generic parameter sets deviate for soil samples in a non-systematic way from the measured results. Replacing Qmax,H1 in generic parameter sets with material-specific values improves the predictions for soil HA significantly. For JGFA, the agreement between the model prediction and data is still not satisfactory after substitution. This is due to a very different pattern of site distribution of JGFA from that of generic FA. For two other soil FAs (FH-14, FH-22 of Milne's database) the generic predictions can be improved significantly with material-specific Qmax,H1. Adjusting also Qmax,H2 to HS material-specific value improves the prediction only slightly further. In practice, Qmax,H1 and Qmax,H2 of HS can be obtained in a relatively simple way by performing one acid–base titration at a given ionic strength and applying the procedure of Lenoir et al. to fit data to NICA equation. Introduction of thus obtained Qmax,H1 and Qmax,H2 into generic parameter sets improves the generic predictions significantly. The functional group contents as obtained by SG-method are not adequate for this purpose.
    Carbon Nanofiber-Supported K2CO3 as an Efficient Low-Temperature Regenerable CO2 Sorbent for Post-Combustion Capture
    Meis, N.N.A.H. ; Frey, A.M. ; Bitter, J.H. ; Jong, K.P. de - \ 2013
    Industrial & Engineering Chemistry Research 52 (2013)36. - ISSN 0888-5885 - p. 12812 - 12818.
    metal-organic frameworks - fixed-bed operations - solid base catalysts - flue-gas - dioxide - adsorption - recovery - adsorbents - sorption - k2co3-on-carbon
    This study focuses on regenerable sorbents for post-combustion CO2 capture at low temperature (373 K). K2CO3 loaded on three different supports, carbon nanofibers (CNF), alumina (¿-Al2O3), and activated carbon (AC), was investigated. K2CO3–CNF revealed excellent properties as CO2 sorbent, displaying capacities of 1.2–1.6 mmol g–1 and fast desorption kinetics at low temperatures (423 K). This temperature was too low to completely regenerate K2CO3–Al2O3 and K2CO3–AC, and consequently, these sorbents lost 8% and 50%, respectively, of their capacity after the first absorption–desorption cycle. K2CO3–CNF could be regenerated to restore 80% of its capacity with a low energy input, estimated at 2–3 GJ/ton CO2, which is competitive to currently used amines.
    Comparison of Tungsten and Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Oleic Acid
    Hollak, S.A.W. ; Gosselink, R.J.A. ; Es, D.S. van; Bitter, J.H. - \ 2013
    ACS Catalysis 3 (2013)12. - ISSN 2155-5435 - p. 2837 - 2844.
    stearic-acid - fatty-acids - ruthenium catalysts - diesel production - reaction pathways - deoxygenation - biodiesel - hydrocarbons - adsorption - oils
    Group 6 (W, Mo) metal carbide catalysts are promising alternatives to hydrodesulfurization (NiMo, CoMo) catalysts and group 10 (Pd) type catalysts in the deoxygenation of vegetable fats/oils. Herein, we report a comparison of carbon nanofiber-supported W2C and Mo2C catalysts on activity, selectivity, and stability for the hydrodeoxygenation of oleic acid to evaluate the catalytic potential for the upgrading of fat/oil feeds. W2C/CNF was more selective toward olefins, whereas Mo2C/CNF was more selective toward paraffins. This was related to the hydrogenation activities of the respective metal carbides. Mo2C/CNF showed higher activity and stability compared with W2C/CNF.
    On the collapse transition of a polymer brush: the case of lateral mobility
    Leermakers, F.A.M. ; Egorov, S.A. - \ 2013
    Soft Matter 9 (2013)12. - ISSN 1744-683X - p. 3341 - 3348.
    terminally attached chains - consistent field-theory - poor solvents - molecular-dynamics - tethered polymers - model - adsorption - interface - surfaces - layers
    We consider a polymer brush composed of end-grafted polymer chains. Classical theory advocates that a worsening of the solvent quality results in a smooth decrease of the brush height from a swollen to a dense brush. We report that a homogeneous brush under poor solvent conditions can have a negative surface pressure, indicating an instability in favour of lateral segregation. Also by using a two-gradient version of the self-consistent field (SCF) theory we show that, in contradiction to the classical result, but in line with the negative pressure, the collapse transition for laterally mobile chains has a first-order character, exemplified by the presence of a compact brush that coexists with a dilute gas of end-grafted chains. The dense brush assumes a pancake shape wherein the chains balance the stretching entropy against surface energies. The height of the pancake scales sub-linearly with the chain length because the local grafting density decreases with increasing chain length. In analogy with wetting studies we discuss how the spreading parameter has an influence on the pancake structure. Accordingly, the height increases with worsening of the solvent quality and decreases with increased affinity for the substrate. The two-phase state is expected in many practical situations
    Self-consistent field predictions for quenched spherical biocompatible triblock copolymer micelle
    Lebouille, J.G.J.L. ; Tuinier, R. ; Vleugels, L.F.W. ; Cohen Stuart, M.A. ; Leermakers, F.A.M. - \ 2013
    Soft Matter 9 (2013)31. - ISSN 1744-683X - p. 7515 - 7525.
    interacting chain molecules - angle neutron-scattering - aqueous-solution - statistical-theory - block-copolymers - micellization - adsorption - biodegradation - microspheres - degradation
    We have used the Scheutjens–Fleer self-consistent field (SF-SCF) method to predict the self-assembly of triblock copolymers with a solvophilic middle block and sufficiently long solvophobic outer blocks. We model copolymers consisting of polyethylene oxide (PEO) as the solvophilic block and poly(lactic-co-glycolic) acid (PLGA) or poly(e-caprolactone) (PCL) as the solvophobic block. These copolymers form structurally quenched spherical micelles provided the solvophilic block is long enough. Predictions are calibrated on experimental data for micelles composed of PCL-PEO-PCL and PLGA-PEO-PLGA triblock copolymers prepared via the nanoprecipitation method. We establish effective interaction parameters that enable us to predict various micelle properties such as the hydrodynamic size, the aggregation number and the loading capacity of the micelles for hydrophobic species that are consistent with experimental findings
    Bending rigidities of surfactant bilayers using self-consistent field theory
    Leermakers, F.A.M. - \ 2013
    Journal of Chemical Physics 138 (2013). - ISSN 0021-9606 - 11 p.
    interacting chain molecules - lipid-bilayers - curvature elasticity - statistical-theory - adsorption - membranes - size - thermodynamics - interface - relevance
    Self-consistent field (SCF) theory is used to find bending moduli of surfactant and lipid bilayers. Recently, we successfully applied low-memory search methods to solve the SCF equations. Using these we are now able to directly evaluate the Gaussian bending modulus for molecularly detailed models of bilayers by evaluating the excess Helmholtz energy of tensionless bilayers in a (part of the) Im3m cubic phase. The result prompted us to reconsider the protocol that has been used thus far to find the mean bending modulus k c and Gaussian bending modulus k¯. With respect to previous predictions, the value of k c is reduced by a factor of two and the Gaussian bending modulus is less negative and much closer to zero. In line with experimental data we now find that k¯can also become positive. In this paper we use the non-ionic surfactants series of the type C n E m for illustration.
    Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain nder critical conditions
    Skvortsov, A.M. ; Leermakers, F.A.M. ; Fleer, G.J. - \ 2013
    Journal of Chemical Physics 139 (2013). - ISSN 0021-9606 - 10 p.
    monte-carlo simulations - linear flexible macromolecules - molecular-dynamics simulations - variable-density model - atomistic simulation - solid interfaces - adsorption - tension - graphite - ends
    In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of floating free chains of concentration f by the self-consistent field (SCF) method. Apart from the grafting, probe chain and floating chains are identical. Most of the results were obtained for a standard SCF model with freely jointed chains on a six-choice lattice, where immediate step reversals are allowed. A few data were generated for a five-choice lattice, where such step reversals are forbidden. These coarse-grained models describe the equilibrium properties of flexible atactic polymer chains at the scale of the segment length. The concentration was varied over the whole range from f = 0 (single grafted chain) to f = 1 (probe chain in the melt). The number of contacts with the surface, average height of the free end and its dispersion, average loop and train length, tail size distribution, end-point and overall segment distributions were calculated for a grafted probe chain as a function of f, for several chain lengths and substrate/polymer interactions, which were varied from strong repulsion to strong adsorption. The computations show that the conformations of the probe chain in the melt do not depend on substrate/polymer interactions and are very similar to the conformations of a single end-grafted chain under critical conditions, and can thus be described analytically. When the substrate/polymer interaction is fixed at the value corresponding to critical conditions, all equilibrium properties of a probe chain are independent of f, over the whole range from a dilute solution to the melt. We believe that the conformations of all flexible chains in the surface region of the melt are close to those of an appropriate single chain in critical conditions, provided that one end of the single chain is fixed at the same point as a chain in the melt.
    Pearl-necklace complexes of flexible polyanions with neutral-cationic diblock copolymers
    Golinska, M.D. ; Wolf, F.A. de; Cohen Stuart, M.A. ; Hernandez Garcia, A. ; Vries, R.J. de - \ 2013
    Soft Matter 9 (2013)28. - ISSN 1744-683X - p. 6406 - 6411.
    polyelectrolyte complexes - core micelles - poor solvent - adsorption - stability - brushes - films
    We study the complexation of very asymmetric diblock copolymers (consisting of a cationic block of 12 lysines connected to a 400 amino acid long hydrophilic polypeptide block with a net charge that is nearly zero) with oppositely charged sodium poly(acrylic acid) (NaPAA) with a range of molar masses between 2 and 1300 kg mol-1. For shorter Na-PAA chains, spherical complex coacervate micelles are formed, but for long Na-PAA chains, with molar masses in excess of 250 kg mol-1, atomic force microscopy indicates the presence of pearl-necklace structures. Complexes most likely consist of only a single NaPAA chain, complexed to multiple diblocks. Hence, the size of the complexes can be fully controlled via the NaPAA molar mass. The occurrence of pearl-necklace complexes at higher NaPAA molar masses is attributed to the packing frustration that arises due to the small size of the cationic block of the diblock copolymers
    Goede waterkwaliteit en meer kansen voor natuur : met immobilisatie van fosfaat door restmaterialen
    Chardon, W.J. ; Groenenberg, J.E. - \ 2013
    landbouwgrond - fosfaatuitspoeling - adsorptie - kaderrichtlijn water - natuurgebieden - agricultural land - phosphate leaching - adsorption - water framework directive - natural areas
    Hoge fosfaatgehalten in landbouwgronden kunnen eutrofiëring van het oppervlaktewater veroorzaken, waardoor overmatige groei van waterplanten en algen optreedt. Met alleen het mestbeleid lukt het niet om de doelstellingen van de Kaderrichtlijn Water (KRW) te bereiken, onder andere als gevolg van de voorraden fosfaat die in de bodem aanwezig zijn. Daarom zijn aanvullende maatregelen noodzakelijk.. Een mogelijke oplossing is de verwijdering van fosfaat in het naar het oppervlaktewater uitstromende water.
    Non-linear surface dilatational rheology as a tool for understanding microstructures of air/water interfaces stabilized by oligofructose fatty acid esters
    Kempen, S.E.H.J. van; Schols, H.A. ; Linden, E. van der; Sagis, L.M.C. - \ 2013
    Soft Matter 9 (2013)40. - ISSN 1744-683X - p. 9579 - 9592.
    air-water-interface - monolayers - layers - shear - viscoelasticity - adsorption - systems - foams
    In this paper, the rheological response of air/water interfaces, stabilized by various oligofructose fatty acid esters, to oscillatory dilatational deformations was studied and compared to the response of interfaces stabilized by sucrose esters. We have followed a traditional approach to surface rheology, where the development of the modulus as a function of time is studied as well as the frequency dependence of the modulus. We also adopted a different approach where we investigate in detail the amplitude dependence of the modulus. Finally, we studied the temperature dependence. We show that for an accurate characterization of the dilatational rheology of fluid-fluid interfaces with a complex microstructure, a protocol should be used that not only involves variations of surface pressure, frequency, and temperature, but also establishes amplitude dependence. We show that Lissajous plots of surface pressure versus deformation can be useful tools to help interpret surface dilatational behavior in terms of interfacial microstructure. The rheological response of interfaces stabilized by oligofructose esters differed significantly from the response of those stabilized by sucrose esters. Sucrose esters behaved like typical low molecular weight surfactants, and gave interfaces with relatively low moduli, a frequency scaling of the dilatational modulus with an exponent close to 0.5, and displayed no asymmetries in Lissajous plots. In contrast, the oligofructose esters gave, depending on the fatty acid tail, relatively high moduli, almost independent of frequency. Significant asymmetries were observed in the Lissajous plots, with strain hardening during compression and strain softening during extension. Our results suggest that the unusual rheological properties of interfaces stabilized by oligofructose esters may be the result of the formation of a two-dimensional soft glass phase by the oligofructose part of the ester.
    Protein Concentration and Protein-Exposed Hydrophobicity as Dominant Parameters Determining the Flocculation of Protein-Stabilized Oil-in-Water Emulsions
    Delahaije, R.J.B.M. ; Wierenga, P.A. ; Nieuwenhuijzen, N.H. van; Giuseppin, M.L.F. ; Gruppen, H. - \ 2013
    Langmuir 29 (2013)37. - ISSN 0743-7463 - p. 11567 - 11574.
    diffusing wave spectroscopy - beta-lactoglobulin - coalescence stability - disjoining pressure - drop size - adsorption - films - ph - interfaces - ovalbumin
    DLVO theory is often considered to be applicable to the description of flocculation of protein-stabilized oil-in-water emulsions. To test this, emulsions made with different globular proteins (ß-lactoglobulin, ovalbumin, patatin, and two variants of ovalbumin) were compared under different conditions (pH and electrolyte concentration). As expected, flocculation was observed under conditions in which the zeta potential is decreased (around the isoelectric point and at high ionic strength). However, the extent of flocculation at higher ionic strength (>50 mM NaCl) decreased with increasing protein-exposed hydrophobicity. A higher exposed hydrophobicity resulted in a higher zeta potential of the emulsion droplets and consequently increased stability against flocculation. Furthermore, the addition of excess protein strongly increased the stability against salt-induced flocculation, which is not described by DLVO theory. In the protein-poor regime, emulsions showed flocculation at high ionic strength (>100 mM NaCl), whereas emulsions were stable against flocculation if excess protein was present. This research shows that the exposed hydrophobicity of the proteins and the presence of excess protein affect the flocculation behavior.
    Protein transfer to membranes upon shape deformation
    Sagis, L.M.C. ; Bijl, E. ; Antono, L. ; Ruijter, N.C.A. de; Valenberg, H.J.F. van - \ 2013
    The European Physical Journal. Special Topics 222 (2013)1. - ISSN 1951-6355 - p. 61 - 71.
    blood-cell deformability - in-water emulsions - fat globule size - interfacial permeability - flow - drops - milk - dissolution - infections - adsorption
    Red blood cells, milk fat droplets, or liposomes all have interfaces consisting of lipid membranes. These particles show significant shape deformations as a result of flow. Here we show that these shape deformations can induce adsorption of proteins to the membrane. Red blood cell deformability is an important factor in several diseases involving obstructions of the microcirculatory system, and deformation induced protein adsorption will alter the rigidity of their membranes. Deformation induced protein transfer will also affect adsorption of cells onto implant surfaces, and the performance of liposome based controlled release systems. Quantitative models describing this phenomenon in biomaterials do not exist. Using a simple quantitative model, we provide new insight in this phenomenon. We present data that show convincingly that for cells or droplets with diameters upwards of a few micrometers, shape deformations induce adsorption of proteins at their interface even at moderate flow rates.
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