| 1. |
- Limpens, J., et al.
(författare)
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Glasshouse vs field experiments : do they yield ecologically similar results for assessing N impacts on peat mosses?
- 2012
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Ingår i: New Phytologist. - : Wiley. - 0028-646X .- 1469-8137. ; 195:2, s. 408-418
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Tidskriftsartikel (refereegranskat)abstract
- Peat bogs have accumulated more atmospheric carbon (C) than any other terrestrial ecosystem today. Most of this C is associated with peat moss (Sphagnum) litter. Atmospheric nitrogen (N) deposition can decrease Sphagnum production, compromising the C sequestration capacity of peat bogs. The mechanisms underlying the reduced production are uncertain, necessitating multifactorial experiments. We investigated whether glasshouse experiments are reliable proxies for field experiments for assessing interactions between N deposition and environment as controls on Sphagnum N concentration and production. We performed a meta-analysis over 115 glasshouse experiments and 107 field experiments. We found that glasshouse and field experiments gave similar qualitative and quantitative estimates of changes in Sphagnum N concentration in response to N application. However, glasshouse-based estimates of changes in production even qualitative assessments diverged from field experiments owing to a stronger N effect on production response in absence of vascular plants in the glasshouse, and a weaker N effect on production response in presence of vascular plants compared to field experiments. Thus, although we need glasshouse experiments to study how interacting environmental factors affect the response of Sphagnum to increased N deposition, we need field experiments to properly quantify these effects.
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| 2. |
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| 3. |
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| 4. |
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| 5. |
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| 6. |
- Limpens, J., et al.
(författare)
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Climatic modifiers of the response to nitrogen deposition in peat-forming Sphagnum mosses : a meta-analysis
- 2011
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Ingår i: New Phytologist. - : Wiley. - 0028-646X .- 1469-8137. ; 191:2, s. 496-507
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Tidskriftsartikel (refereegranskat)abstract
- Peatlands in the northern hemisphere have accumulated more atmospheric carbon (C) during the Holocene than any other terrestrial ecosystem, making peatlands long-term C sinks of global importance. Projected increases in nitrogen (N) deposition and temperature make future accumulation rates uncertain. Here, we assessed the impact of N deposition on peatland C sequestration potential by investigating the effects of experimental N addition on Sphagnum moss. We employed meta-regressions to the results of 107 field experiments, accounting for sampling dependence in the data. We found that high N loading (comprising N application rate, experiment duration, background N deposition) depressed Sphagnum production relative to untreated controls. The interactive effects of presence of competitive vascular plants and high tissue N concentrations indicated intensified biotic interactions and altered nutrient stochiometry as mechanisms underlying the detrimental N effects. Importantly, a higher summer temperature (mean for July) and increased annual precipitation intensified the negative effects of N. The temperature effect was comparable to an experimental application of almost 4 g N m(-2) yr(-1) for each 1 degrees C increase. Our results indicate that current rates of N deposition in a warmer environment will strongly inhibit C sequestration by Sphagnum-dominated vegetation.
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| 7. |
- Hansson, Petra M., et al.
(författare)
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Frictional forces between hydrophilic and hydrophobic particle coated nanostructured surfaces
- 2013
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 15:41, s. 17893-17902
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Tidskriftsartikel (refereegranskat)abstract
- Friction forces have long been associated with the famous Amontons' rule that states that the friction force is linearly dependent on the applied normal load, with the proportionality constant being known as the friction coefficient. Amontons' rule is however purely phenomenological and does not in itself provide any information on why the friction coefficient is different for different material combinations. In this study, friction forces between a colloidal probe and nanostructured particle coated surfaces in an aqueous environment exhibiting different roughness length scales were measured by utilizing the atomic force microscope (AFM). The chemistry of the surfaces and the probe was varied between hydrophilic silica and hydrophobized silica. For hydrophilic silica surfaces, the friction coefficient was significantly higher for the particle coated surfaces than on the flat reference surface. All the particle coated surfaces exhibited similar friction coefficients, from which it may be concluded that the surface geometry, and not the roughness amplitude per se, influenced the measured friction. During measurements with hydrophobic surfaces, strong adhesive forces related to the formation of a bridging air cavity were evident from both normal force and friction force measurements. In contrast to the frictional forces between the hydrophilic surfaces, the friction coefficient for hydrophobic surfaces was found to depend on the surface structure and we believe that this dependence is related to the restricted movement of the three-phase line of the bridging air cavity. For measurements using a hydrophobic surface and a hydrophilic probe, the friction coefficient was significantly smaller compared to the two homogeneous systems. A layer of air or air bubbles on the hydrophobic surface working as a lubricating layer is a possible mechanism behind this observation.
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| 8. |
- Pilkington, Georgia A., et al.
(författare)
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Amontonian frictional behaviour of nanostructured surfaces
- 2011
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 13, s. 9318-9326
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Tidskriftsartikel (refereegranskat)abstract
- With nanotextured surfaces and interfaces increasingly being encountered in technological and biomedical applications, there is a need for a better understanding of frictional properties involving such surfaces. Here we report friction measurements of several nanostructured surfaces using an Atomic Force Microscope (AFM). These nanostructured surfaces provide well defined model systems on which we have tested the applicability of Amontons' laws of friction. Our results show that Amontonian behaviour is observed with each of the surfaces studied. However, no correlation has been found between measured friction and various surface roughness parameters such as average surface roughness (Ra) and root mean squared (rms) roughness. Instead, we propose that the friction coefficient may be decomposed into two contributions, i.e., μ = μ0 + μg, with the intrinsic friction coefficient μ0 accounting for the chemical nature of the surfaces and the geometric friction coefficient μg for the presence of nanotextures. We have found a possible correlation between μg and the average local slope of the surface nanotextures.
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| 9. |
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| 10. |
- Bodvik, Rasmus, et al.
(författare)
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Aggregation of modified celluloses in aqueous solution : transition from methylcellulose to hydroxypropylmethylcellulose solution properties induced by a low molecular weight oxyethylene additive
- 2012
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 28:38, s. 13562-13569
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Tidskriftsartikel (refereegranskat)abstract
- Temperature effects on viscosity and aggregation behaviour of aqueous solutions of three different cellulose ethers: methylcellulose (MC), hydroxypropylmethylcellulose (HPMC) and ethyl(hydroxyethyl)cellulose (EHEC), were investigated using viscosity and dynamic light scattering measurements as well as Cryo-TEM. In all cases increasing temperature reduces the solvent quality of water, which induces aggregation. It was found that the aggregation rate followed the order EHEC > HPMC > MC, suggesting that cellulose ethers containing some bulky and partly hydrophilic substituents assemble into large aggregates more readly than methylcellulose. This finding is discussed in terms of the organization of the structures formed by the different cellulose ethers. The temperature-dependent association behavior of cellulose ethers was also investigated in a novel way by adding diethyleneglycolmonobutylether (BDG) to methylcellulose aqueous solutions. When the concentration of BDG was at and above 5 wt%, methylcellulose adopted HPMC-like solution behaviour. In particular, a transition temperature where the viscosity was decreasing, prior to increasing at higher temperatures, appeared and the aggregation rate increased. This observation is rationalized by the ability of the amphiphilic BDG to accumulate at non-polar interfaces, and thus also to associate with hydrophobic regions of methylcellulose. In effect BDG is suggested to act as a physisorbed hydrophilic and bulky substituent inducing similar constraints on aggregation as the chemically attached hydroxypropyl groups in HPMC and oligo(ethyleneoxide) chains in EHEC.
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| 11. |
- Bodvik, Rasmus, et al.
(författare)
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Temperature-dependent adsorption of cellulose ethers on silica and hydrophobized silica immersed in aqueous polymer solution
- 2011
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Ingår i: RSC ADVANCES. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 1:2, s. 305-314
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Tidskriftsartikel (refereegranskat)abstract
- The influence of temperature on adsorption and the adsorbed layer properties of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) were investigated on silica and hydrophobized silica surfaces immersed in aqueous polymer solution. To achieve a concise understanding a quartz crystal microbalance with dissipation, ellipsometry, and atomic force microscopy imaging were employed. These techniques provide complimentary information on the structure, mass and viscoelastic properties of the polymer layers. Adsorption was first allowed at 25 degrees C. Next, the temperature was increased step-wise up to 50 degrees C and then decreased again. This procedure highlights the temperature dependence of the adsorbed material, as well as the hysteresis in the adsorption due to temperature cycling. A change in temperature not only affects the adsorbed amount, but also the properties of the layer as illustrated by measurements of its water content, thickness and viscoelasticity.
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| 12. |
- Bodvik, Rasmus, et al.
(författare)
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Temperature-Dependent Competition between Adsorption and Aggregation of a Cellulose Ether-Simultaneous Use of Optical and Acoustical Techniques for Investigating Surface Properties
- 2012
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 28:25, s. 9515-9525
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Tidskriftsartikel (refereegranskat)abstract
- Adsorption of the temperature-responsive polymer hydroxypropylmethylcellulose (HPMC) from an aqueous solution onto hydrophobized silica was followed well above the bulk instability temperature (T-2) in temperature cycle experiments. Two complementary techniques, QCM-D and ellipsometry, were utilized simultaneously to probe the same substrate immersed in polymer solution. The interfacial processes were correlated with changes in polymer aggregation and viscosity of polymer solutions, as monitored by light scattering and rheological measurements. The simultaneous use of ellipsometry and QCM-D, and the possibility to follow layer properties up to 80 degrees C, well above the T-2 temperature, are both novel developments. A moderate increase in adsorbed amount with temperature was found below T-2, whereas a significant increase in the adsorbed mass and changes in layer properties were observed around the T-2 temperature where the bulk viscosity increases significantly. Thus, there is a clear correlation between transition temperatures in the adsorbed layer and in bulk solution, and we discuss this in relation to a newly proposed model that considers competition between aggregation and adsorption/deposition. A much larger temperature response above the T-2 temperature was found for adsorbed layers of HPMC than for layers of methyl cellulose. Possible reasons for this are discussed.
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| 13. |
- Bodvik, Rasmus, et al.
(författare)
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Temperature responsive surface layers of modified celluloses
- 2011
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 13:10, s. 4260-4268
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Tidskriftsartikel (refereegranskat)abstract
- The temperature-dependent properties of pre-adsorbed layers of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) were investigated on silica and hydrophobized silica surfaces. Three different techniques, quartz crystal microbalance with dissipation monitoring, ellipsometry, and atomic force microscopy imaging, were used, providing complementary and concise information on the structure, mass and viscoelastic properties of the polymer layer. Adsorption was conducted at 25 degrees C, followed by a rinsing step. The properties of such pre-adsorbed layers were determined as a function of temperature in the range 25 degrees C to 50 degrees C. It was found that the layers became more compact with increasing temperature and that this effect was reversible, when decreasing the temperature. The compaction was more prominent for MC, as shown in the AFM images and in the thickness data derived from the QCM analysis. This is consistent with the fact that the phase transition temperature is lower, in the vicinity of 50 degrees C, for MC than for HPMC. The water content of the adsorbed layers was found to be high, even at the highest temperature, 50 degrees C, explored in this investigation.
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| 14. |
- Dédinaité, Andra, et al.
(författare)
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Friction in aqueous media tuned by temperature-responsive polymer layers
- 2010
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Ingår i: SOFT MATTER. - : Royal Society of Chemistry (RSC). - 1744-683X .- 1744-6848. ; 6:11, s. 2489-2498
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Tidskriftsartikel (refereegranskat)abstract
- An atomic force microscope colloidal probe technique has been employed to probe normal and friction forces between silica surfaces coated with adsorbed layers of a diblock copolymer of the composition poly(N-isopropylacrylamide)(48)-block-poly(3-acrylamidopropyl)trimethyla mmonium chloride)(20), abbreviated PNIPAAM(48)-b-PAMPTMA(+)(20). The interactions between the PNIPAAM(48)-b-PAMPTMA(+)(20)-coated surfaces across a 0.1 mM NaCl (pH 6) solution at 25 degrees C are purely repulsive, due to a combination of steric and electrostatic double-layer forces. However, when the temperature is increased to 35 degrees C, and subsequently to 45 degrees C, an attractive force develops at short separations due to the unfavourable PNIPAAM-water interaction at these temperatures. The temperature-dependent polymer-water interaction has implications for the friction force between the layers. At 25 degrees C a frictional force that increases linearly with increasing load is observed once the surfaces are brought into close contact. At higher temperatures significantly higher friction forces appear as a consequence of attractive segment-segment interactions. Further, a clearly expressed hysteresis between friction forces encountered on loading and unloading is detected. Our results demonstrate that both normal and friction forces between surfaces can be controlled by temperature changes when temperature-responsive polymers are employed, and friction forces can be adjusted as required from low to high.
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| 15. |
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| 16. |
- Dunér, Gunnar, et al.
(författare)
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Nanomechanical mapping of a high curvature polymer brush grafted from a rigid nanoparticle
- 2012
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Ingår i: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-683X .- 1744-6848. ; 8:32, s. 8312-8320
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Tidskriftsartikel (refereegranskat)abstract
- Analysis of interaction forces when probing a silica core-polyelectrolyte brush shell nanoparticle, adsorbed on a silica substrate and bathed by aqueous electrolyte solution, with an ultrasharp atomic force microscopy (AFM) tip provides a spatially resolved map of heterogeneous mechanical properties across the nanoparticle. The deformation of the brush is mainly compressive when probed directly above the nanoparticle centre and mainly deflective when probed at a finite horizontal distance away from the centre. The brush is significantly stiffer against compression than against deflection, and ionization of the brush has a greater stiffening effect against compression than deflection. Whereas a height image of the core-shell nanoparticle was unremarkable, showing a monotonic decrease in height with increasing horizontal distance from the centre, brush deformation, energy dissipation and adhesion displayed local minima over the centre and maxima at a finite horizontal distance away from the centre, corresponding to a position near the rigid core nanoparticle edge. The different response to brush deformation depending on the angle of probing is relevant to the interactions of brush-decorated macroscopic surfaces with submicrometer roughness and to the interactions of brush-decorated nanoparticles with ultrafine structures in their environments.
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| 17. |
- Hansson, P. M., et al.
(författare)
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Effect of local curvature on the interaction between hydrophobic surfaces
- 2010
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Ingår i: Nanotechnology 2010: Advanced Materials, CNTs, Particles, Films and Composites - Technical Proceedings of the 2010 NSTI Nanotechnology Conference and Expo, NSTI-Nanotech 2010. - 9781439834015 ; , s. 61-64
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Konferensbidrag (refereegranskat)abstract
- Surface structure, including roughness and chemical heterogeneities, is known to be of importance for the surface interaction forces observed between hydrophobic and superhydrophobic surfaces. In this study, silica particles have been used to prepare structured particulated surfaces with a controlled roughness using Langmuir-Blodgett deposition or a drop coating technique. The surfaces were characterized by SEM and AFM. The AFM colloidal probe technique was employed for probing the interaction between a micro-size hydrophobic particle and hydrophobic surfaces with a sintered and silanized nano-sized silica particle monolayer. These measurements indicate that the adhesion force is increased by a decrease in particle size. Larger roughness gives larger crevices on the surface and more air/vapor accumulation but the capillary growth is impaired since the three-phase line (solid-liquid-air) has to move over a longer distance with an increase in the size of the surface features.
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| 18. |
- Hansson, Petra M., et al.
(författare)
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Effect of surface depressions on wetting and interactions between hydrophobic pore array surfaces
- 2012
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 28:30, s. 11121-11130
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Tidskriftsartikel (refereegranskat)abstract
- The surface structure is known to significantly affect the long-range capillary forces between hydrophobic surfaces in aqueous solutions. It is, however, not clear how small depressions in the surface will affect the interaction. To clarify this, we have used the AFM colloidal probe technique to measure interactions between hydrophobic microstructured pore array surfaces and a hydrophobic colloidal probe. The pore array surfaces were designed to display two different pore spacings, 1.4 and 4.0 ÎŒm, each with four different pore depths ranging from 0.2 to 12.0 ÎŒm. Water contact angles measured on the pore array surfaces are lower than expected from the Cassie-Baxter and Wenzel models and not affected by the pore depth. This suggests that the position of the three-phase contact line, and not the interactions underneath the droplet, determines the contact angle. Confocal Raman microscopy was used to investigate whether water penetrates into the pores. This is of importance for capillary forces where both the movement of the three-phase contact line and the situation at the solid/liquid interface influence the stability of bridging cavities. By analyzing the shape of the force curves, we distinguish whether the cavity between the probe and the surfaces was formed on a flat part of the surface or in close proximity to a pore. The pore depth and pore spacing were both found to statistically influence the distance at which cavities form as surfaces approach each other and the distance at which cavities rupture during retraction.
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| 19. |
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| 20. |
- Hansson, Petra M., 1983-, et al.
(författare)
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Hydrophobic pore array surfaces : Wetting and interaction forces in water/ethanol mixtures
- 2013
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Ingår i: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 396, s. 278-286
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Tidskriftsartikel (refereegranskat)abstract
- Interactions between and wetting behavior of structured hydrophobic surfaces using different concentrations of water/ethanol mixtures have been investigated. Silica surfaces consisting of pore arrays with different pore spacings and pore depths were made hydrophobic by silanization. Their static and dynamic contact angles were found to be independent of the pore depth while fewer pores on the surface, i.e. a closer resemblance to a flat surface, gave a lower contact angle. As expected, a higher amount of ethanol facilitated wetting on all the surfaces tested. Confocal Raman microscopy measurements proved both water and ethanol to penetrate into the pores. AFM colloidal probe force measurements clearly showed that formation of air cavitation was hindered between the hydrophobic surfaces in presence of ethanol, and an increase in ethanol concentration was followed by a smaller jump-in distance and a weaker adhesion force. On separation, an immediate jump-out of contact occurred. The measured forces were interpreted as being due to capillary condensation of ethanol between the surfaces giving rise to very unstable cavities immediately rupturing on surface separation.
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| 21. |
- Hansson, Petra M., et al.
(författare)
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Influence of Surface Topography on the Interactions between Nanostructured Hydrophobic Surfaces
- 2012
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 28:21, s. 8026-8034
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Tidskriftsartikel (refereegranskat)abstract
- Nanostructured particle coated surfaces, with hydrophobized particles arranged in close to hexagonal order and of specific diameters ranging from 30 nm up to 800 nm, were prepared by Langmuir-Blodgett deposition followed by silanization. These surfaces have been used to study interactions between hydrophobic surfaces and a hydrophobic probe using the AFM colloidal probe technique. The different particle coated surfaces exhibit similar water contact angles, independent of particle size, which facilitates studies of how the roughness length scale affects capillary forces (previously often referred to as "hydrophobic interactions") in aqueous solutions. For surfaces with smaller particles (diameter < 200 nm), an increase in roughness length scale is accompanied by a decrease in adhesion force and bubble rupture distance. It is suggested that this is caused by energy barriers that prevent the motion of the three-phase (vapor/liquid/solid) line over the surface features, which counteracts capillary growth. Some of the measured force curves display extremely long-range interaction behavior with rupture distances of several micrometers and capillary growth with an increase in volume during retraction. This is thought to be a consequence of nanobubbles resting on top of the surface features and an influx of air from the crevices between the particles on the surface.
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| 22. |
- Hansson, Petra M., et al.
(författare)
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Robust Hydrophobic Surfaces Displaying Different Surface Roughness Scales While Maintaining the Same Wettability
- 2011
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 27:13, s. 8153-8159
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Tidskriftsartikel (refereegranskat)abstract
- A range of surfaces coated with spherical silica particles, covering the size range from nanometer to micrometer, have been produced using Langmuir-Blodgett (LB) deposition. The particles were characterized both in suspension and in the Langmuir trough to optimize the surface preparation procedure. By limiting the particle aggregation and surface layer failures during the preparation steps, well-defined monolayers with a close-packed structure have been obtained for all particle sizes. Thus, this procedure led to structured surfaces with a characteristic variation in the amplitude and spatial roughness parameters. In order to obtain robust surfaces, a sintering protocol and an AFM-based wear test to determine the stability of the deposited surface layer were employed. Hydrophobization of the LB films followed by water contact angle measurements showed, for all tested particle sizes, the same increase in contact angle compared to the contact angle of a flat hydrophobic surface. This indicates nearly hexagonal packing and gives evidence for nearly, complete surface wetting of the surface features.
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| 23. |
- Liu, Chao, et al.
(författare)
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Charge regulation and energy dissipation while compressing and sliding a cross-linked chitosan hydrogel layer
- 2015
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Ingår i: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 443, s. 162-169
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Tidskriftsartikel (refereegranskat)abstract
- Interactions between a silica surface and a surface coated with a grafted cross-linked hydrogel made from chitosan/PAA multilayers are investigated, utilizing colloidal probe atomic force microscopy. Attractive double-layer forces are found to dominate the long-range interaction over a broad range of pH and ionic strength conditions. The deduced potential at the hydrogel/aqueous interface is found to be very low. This situation is maintained in the whole pH-range investigated, even though the degree of protonation of chitosan changes significantly. This demonstrates that pH-variations change the concentration of counterions within the hydrogel to keep the interior close to uncharged, which is similar to what has been observed for polyelectrolyte brushes. Changes in pH and ionic strength affect the adhesion force and the friction force between the silica surface and the hydrogel layer, but not the friction coefficient. This suggests that the main energy dissipation mechanism arises from processes occurring within the hydrogel layer, rather than at the silica/hydrogel interface, and we suggest that it is related to stretching of polymer chains between the cross-linking points. We also find that an increased cross-linking density, from 40% to 100%, in the hydrogel reduces the friction coefficient.
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| 24. |
- Liu, Chao, et al.
(författare)
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Surface Grafted Chitosan Gels : Part II. Gel Formation and Characterization
- 2014
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 30:29, s. 8878-8888
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Tidskriftsartikel (refereegranskat)abstract
- Responsive biomaterial hydrogels attract significant attention due to their biocompatibility and degradability. In order to make chitosan based gels, we first graft one layer of chitosan to silica, and then build a chitosan/poly(acrylic acid) multilayer using the layer-by-layer approach. After cross-linking the chitosan present in the polyelectrolyte multilayer, poly(acrylic acid) is partly removed by exposing the multilayer structure to a concentrated carbonate buffer solution at a high pH, leaving a surface-grafted cross-linked gel. Chemical cross-linking enhances the gel stability against detachment and decomposition. The chemical reaction between gluteraldehyde, the cross-linking agent, and chitosan was followed in situ using total internal reflection Raman (TIRR) spectroscopy, which provided a molecular insight into the complex reaction mechanism, as well as the means to quantify the cross-linking density. The amount of poly(acrylic acid) trapped inside the surface grafted films was found to decrease with decreasing cross-linking density, as confirmed in situ using TIRR, and ex situ by Fourier transform infrared (FTIR) measurements on dried films. The responsiveness of the chitosan-based gels with respect to pH changes was probed by quartz crystal microbalance with dissipation (QCM-D) and TIRR. Highly cross-linked gels show a small and fully reversible behavior when the solution pH is switched between pH 2.7 and 5.7. In contrast, low cross-linked gels are more responsive to pH changes, but the response is fully reversible only after the first exposure to the acidic solution, once an internal restructuring of the gel has taken place. Two distinct plc's for both chitosan and poly(acrylic acid), were determined for the cross-linked structure using TIRR. They are associated with populations of chargeable groups displaying either a bulk like dissociation behavior or forming ionic complexes inside the hydrogel film.
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| 25. |
- Liu, Chao, et al.
(författare)
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Surface Grafted Chitosan Gels : Part I. Molecular Insight into the Formation of Chitosan and Poly(acrylic acid) Multi layers
- 2014
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 30:29, s. 8866-8877
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Tidskriftsartikel (refereegranskat)abstract
- Composite polyelectrolyte multilayers of chitosan and low molecular weight poly(acrylic acid) (PAA) have been assembled by sequential adsorption as a first step toward building a surface anchored chitosan gel. Si lane chemistry was used to graft the first chitosan layer to prevent film detachment and decomposition. The assembly process is characterized by nonlinear growth behavior, with different adsorption kinetics for chitosan and PAP.. In situ analysis of the multilayer by means of surface sensitive total internal reflection Raman (TIRR) spectroscopy, combined with target factor analysis of the spectra, provided information regarding composition, including water content, and ionization state of weak acidic and basic groups present in the thin composite film. Low molecular weight PAA, mainly in its protonated form, diffuses into and out of the composite film during adsorption and rinsing steps. The higher molecular weight chitosan shows a similar behavior, although to a much lower extent. Our data demonstrate that the charged monomeric units of chitosan are mainly compensated by carboxylate ions from PAP.. Furthermore, the morphology and mechanical properties of the multilayers were investigated in situ using atomic force microscopy operating in PeakForce tapping mode. The multilayer consists of islands that grow in lateral dimension and height during the build-up process, leading to close to exponentially increasing roughness with deposition number. Both diffusion in and out of at least one of the two components (PAA) and the island-like morphology contribute to the nonlinear growth of chitosan/PAA multilayers.
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| 26. |
- Mizuno, Hiroyasu, et al.
(författare)
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Adhesive properties and sacrificial bonds in gastroliths of red-clawlobster measured by colloidal probe atomic force microscopy
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The adhesive properties of gastroliths of red claw lobsters (Cherax quadricarinatus) have been quantified using colloidal probe atomic force microscopy. Sequential detachment and large adhesion energies where observed between native gastrolith substrates and colloidal probes consisting of microparticles of heavily demineralized gastrolith that consists primarily of chitin and calcium carbonate hemispheres. The sequential detachment behavior was absent when the soluble proteins have been removed from gastrolith substrates and the adhesive energy is reduced by more than two orders of magnitude. The sacrificial bonds that provide the large adhesion energies were inferred to multifunctional gastrolith proteins that are able to bind to both chitin and calcium carbonate.
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| 27. |
- Olanya, Geoffrey, et al.
(författare)
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Protein Interactions with Bottle-Brush Polymer Layers : Effect of Side Chain and Charge Density Ratio Probed by QCM-D and AFM
- 2010
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Ingår i: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 349:1, s. 265-274
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Tidskriftsartikel (refereegranskat)abstract
- Silica surfaces were coated with a range of cationic bottle-brush polymers with 45 units long poly(ethylene oxide) side chains, and their efficiency in reducing protein adsorption was probed by QCM-D, reflectometry and AFM. Preadsorbed layers formed by bottle-brush polymers with different side chain to charge ratio was exposed to two proteins with different net charge, lysozyme and BSA. The reduction in protein adsorption was found to depend on both the type of protein and on the nature of the polyelectrolyte layer. The most pronounced reduction in protein adsorption was achieved when the fraction of charged backbone segments was in the range 0.25-0.5 equivalent to a fraction of poly(ethylene oxide) side chains of 0.75-0.5. It was concluded that these polymers have enough electrostatic attachment points to ensure a strong binding to the surface, and at the same time a sufficient amount of poly(ethylene oxide) side chains to counteract protein adsorption. In contrast, a layer formed by a highly charged polyelectrolyte without side chains was unable to resists protein adsorption. On such a layer the adsorption of negatively charged BSA was strongly enhanced, and positively charged lysozyme adsorbed to a similar extent as to bare silica. AFM colloidal probe force measurement between silica surfaces with preadsorbed layers of bottle-brush polymers were conducted before and after exposure to BSA and lysozyme to gain insight into how proteins were incorporated in the bottle-brush polymer layers.
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| 28. |
- Quignon, Benoit, et al.
(författare)
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Sustained Frictional Instabilities on Nanodomed Surfaces : Stick Slip Amplitude Coefficient
- 2013
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 7:12, s. 10850-10862
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the frictional properties of nanostructured surfaces is important because of their increasing application in modem minlaturized devices. In this work, lateral force microscopy was used to study the frictional properties between AFM nanotip and surfaces bearing well-defined ranging from tens to hundreds of nanometers. Our results show that the average lateral force varied linearly with applied load, as described by Amontons' first law of friction, although no direct correlation between the sample topographic properties and their measured friction coeffidents was identified. Furthermore, all the nanodomed textures exhibited pronounced osdllations in the shear traces, similar to the dassic stick slip behavior, under all the shear velocities and load regimes studied. That is, the nanotextured topography led to sustained frictional instabilities, effectively with no contact frictional sliding. The amplitude of the stick slip oscillations, ab was found to correlate with the topographic properties of the surfaces and scale linearly with the applied load. In line with the friction coefficient, we define the slope of this linear plot as the stick slip amplitude coeffident (SSAC). We suggest that such stick slip behaviors are characteristics of surfaces with nanotextures and that such local frictional instabilities have important implications to surface damage and wear. We thus propose that the shear characteristics of the nanodomed surfaces cannot be fully described by the framework of Amontons' laws of friction and that additional parameters (e.g., a, and SSAQ are required, when their friction, lubrication, and wear properties are important considerations in related nanodevices.
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| 29. |
- Sandbaumhüter, Friederike A., et al.
(författare)
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Stereoselective methadone disposition after administration of racemic methadone to anesthetized Shetland ponies assessed by capillary electrophoresis
- 2021
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Ingår i: Electrophoresis. - : John Wiley & Sons. - 0173-0835 .- 1522-2683. ; 42:17-18, s. 1826-1831
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Tidskriftsartikel (refereegranskat)abstract
- The enantioselectivity of the pharmacokinetics of methadone was investigated in anesthetized Shetland ponies after a single intravenous (0.5 mg/kg methadone hydrochloride; n = 6) or constant rate infusion (0.25 mg/kg bolus followed by 0.25 mg/kg/h methadone hydrochloride; n = 3) administration of racemic methadone. Plasma concentrations of l-methadone and d-methadone and their major metabolites, l- and d-2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), respectively, were analyzed by CE with highly sulfated gamma-cyclodextrin as chiral selector and electrokinetic analyte injection from liquid/liquid extracts prepared at alkaline pH. In both trials, the d-methadone concentrations were lower than those of l-methadone and the d-EDDP levels were lower than those of L-EDDP. For the case of a single intravenous bolus injection, the plasma concentration versus time profile of methadone enantiomers was analyzed with a two-compartment pharmacokinetic model. l-methadone showed a slower elimination rate constant, a lower body clearance, and a smaller steady-state volume of distribution than d-methadone. d-methadone and d-EDDP were eliminated faster than their respective l-enantiomers. This is the first study that outlines that the disposition of racemic methadone administered to anesthetized equines is enantioselective.
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| 30. |
- Thormann, Esben, et al.
(författare)
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Amontonian friction induced by flexible surface features on microstructured silicon
- 2011
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 3:9, s. 3432-3439
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Tidskriftsartikel (refereegranskat)abstract
- Friction between nonadhering sliding surfaces are normally described by Amontons' law, which states that there exists a linear relationship between the friction force and the normal applied load and that the friction force is independent of the macroscopic contact area between the surfaces and the sliding velocity. In this study we have measured friction as a function of applied load between a spherical silica particle and a microstructured silicon surface consisting of arrays of vertical microneedles, and we have challenged Amontons' law by changing the size of the silica particle and the sliding velocity. First, when looking at the friction as a function of time for a given applied load, the friction force was observed to oscillate with a period related to the spacing between the microneedles when using a small silica particle, whereas the friction force exhibited a more random variation when a larger silica particle was used. The oscillation in the friction force is a direct evidence for bending and release of individual microneedles and the observation illustrates that the energy dissipating mechanism becomes hidden in the friction data when the dimensions of the sliding body becomes much larger than the length scale of the surface features causing the friction. Second, when looking at the average friction force as a function of applied load we find, in accordance with Amontons' law, a linear relationship between the friction force and the applied load and the friction force is independent of both the size of the sliding silica particle and of the sliding velocity. One exception from this, however, was observed when sliding a small silica particle at low velocity, where a deviation from Amontons' law was noticed. The deviation from Amontons' law is suggested to be attributed to a change in the energy dissipating mechanism giving rise to the friction force. In light of that it is suggested that Amontons' law only is valid as long as the main energy dissipating mechanism does not change with the applied load. To get a better understanding of the general validity of Amontons' law, our results were evaluated against different microscopic models.
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| 31. |
- Thormann, Esben, et al.
(författare)
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Embedded proteins and sacrificial bonds provide the strong adhesive properties of gastroliths
- 2012
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 4:13, s. 3910-3916
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Tidskriftsartikel (refereegranskat)abstract
- The adhesive properties of gastroliths from a freshwater crayfish (Cherax quadricarinatus) were quantified by colloidal probe atomic force microscopy (AFM) between heavily demineralized gastrolith microparticles and gastrolith substrates of different composition. Combined AFM and transmission electron microscopy studies demonstrated that the sequential detachment and large adhesion energies that characterise the adhesive behaviour of a native gastrolith substrate are dominated by sacrificial bonds between chitin fibres and between chitin fibres and CaCO3. The sacrificial bonds were shown to be strongly related to the gastrolith proteins and when the majority of these proteins were removed by ethylenediaminetetraacetic acid (EDTA), the sequential detachment disappeared and the adhesive energy was reduced by more than two orders of magnitude.
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| 32. |
- Thormann, Esben, et al.
(författare)
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How to measure forces with atomic force microscopy without significant influence from nonlinear optical lever sensitivity
- 2009
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Ingår i: Review of Scientific Instruments. - : AIP Publishing. - 0034-6748 .- 1089-7623. ; 80:9
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Tidskriftsartikel (refereegranskat)abstract
- In an atomic force microscope AFM , the force is normally sensed by measuring the deflection of a cantilever by an optical lever technique. Experimental results show a nonlinear relationship between the detected signal and the actual deflection of the cantileve, which is widely ignored in literature. In this study we have designed experiments to investigate different possible reasons for this nonlinearity and compared the experimental findings with calculations. It is commonly assumed that this nonlinearity only causes problems for extremely large cantilever deflections. However, our results show that the nonlinear detector response might influence many AFM studies where soft or short cantilevers are used. Based on our analysis we draw conclusions of the main reason for the nonlinearity and suggest a rule of thumb for which cantilevers one should use under different experimental conditions.
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| 33. |
- Thormann, Esben, et al.
(författare)
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Probing material properties of polymeric surface layers with tapping mode AFM : Which cantilever spring constant, tapping amplitude and amplitude set point gives good image contrast and minimal surface damage?
- 2010
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Ingår i: Ultramicroscopy. - : Elsevier BV. - 0304-3991 .- 1879-2723. ; 110:4, s. 313-319
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Tidskriftsartikel (refereegranskat)abstract
- A phase shift between the oscillatory motion and drive motion of an AFM-cantilever used for tapping mode AFM imaging can be related to adhesive and elastic properties of surface layers. In this study it was studied how optimal contrast between hard and soft surface layers can be achieved while minimizing the surface damage. This was investigated by performing classical force-distance measurements while driving the cantilever as in tapping mode imaging. The amplitude and phase response as a function of the average tip-surface separation was recorded. Five different cantilevers with a wide range of spring constants and four different tapping amplitudes were investigated and compared. Based on these experiments it is concluded that too stiff cantilever, high free tapping amplitude and low amplitude set point value often lead to surface damage, while too low spring constant and low free tapping amplitude result in poor phase image contrast. Intermediate values where little surface damage and significant image contrast are obtained were identified. In all cases it was observed that the best image contrast was obtained when the amplitude set point was chosen such that the amplitude during imaging was reduced to approximately 50% of the free amplitude.
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| 34. |
- Thormann, Esben, et al.
(författare)
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Surface forces and friction between non-polar surfaces coated by temperature-responsive methylcellulose
- 2014
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Ingår i: Colloids and Surfaces A. - : Elsevier BV. - 0927-7757 .- 1873-4359. ; 441, s. 701-708
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Tidskriftsartikel (refereegranskat)abstract
- Methylcellulose is a heterogeneous polymer that exposes both methyl groups and -OH-groups to the solution, and the solvent quality of water for methylcellulose deceases with increasing temperature. In bulk solution this leads to aggregation into fibrils at high temperatures. In this report we address how temperature affects adsorbed layers of methylcellulose on hydrophobized silica surfaces in contact with an aqueous methylcellulose solution. The layers were imaged using PeakForce tapping mode atomic force microscopy, in order to determine how the additional adsorption that occurs with increasing temperature affects the layer structure. Surface force and friction measurements were carried out using the AFM colloidal probe method. The data demonstrate that the normal surface forces were rather insensitive to temperature, whereas the friction forces changed significantly with increasing temperature. At low loads the friction increases with increasing temperature, whereas at high loads the reverse is observed. These findings are discussed in terms of how the worsening of the solvent condition affects the aggregation state in the adsorbed layer, and the polymer-surface affinity.
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| 35. |
- Thormann, Esben, et al.
(författare)
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Tuning structural forces between silica surfaces by temperature-induced micellization of responsive block copolymers
- 2010
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 12:36, s. 10730-10735
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Tidskriftsartikel (refereegranskat)abstract
- The aim of this study is to demonstrate a method to control interactions between two surfaces by the use of a responsive solution. This was done by performing AFM-based force measurements between two silica surfaces immersed in an aqueous solution of thermo-responsive Pluronics P85 block copolymers. For this system we demonstrate that one can switch between a situation where no long-range forces are acting between the surfaces to a situation where a long-range structural force, oscillating between attractive and repulsive force regimes, is controlling the surface interaction. This shift in behavior is caused by a long-range order introduced by temperature-induced micellization of the block copolymers and is thus simply achieved by changing the temperature from below to above the micellization temperature. We propose that the use of micelle-forming responsive block copolymers is a general method for reversibly controlling surface interactions by a temperature switch. Since the force control is achieved by changes occurring in bulk solution, the nature of the surfaces is expected to play only a relative minor role.
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