| 1. |
- An, Junxue, et al.
(author)
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Effect of solvent quality and chain density on normal and frictional forces between electrostatically anchored thermoresponsive diblock copolymer layers
- 2017
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In: Journal of Colloid and Interface Science. - : Academic Press. - 0021-9797 .- 1095-7103. ; 487, s. 88-96
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Journal article (peer-reviewed)abstract
- Equilibration in adsorbing polymer systems can be very slow, leading to different physical properties at a given condition depending on the pathway that was used to reach this state. Here we explore this phenomenon using a diblock copolymer consisting of a cationic anchor block and a thermoresponsive block of poly(2-isopropyl-2-oxazoline), PIPOZ. We find that at a given temperature different polymer chain densities at the silica surface are achieved depending on the previous temperature history. We explore how this affects surface and friction forces between such layers using the atomic force microscope colloidal probe technique. The surface forces are purely repulsive at temperatures <40 °C. A local force minimum at short separation develops at 40 °C and a strong attraction due to capillary condensation of a polymer-rich phase is observed close to the bulk phase separation temperature. The friction forces decrease in the cooling stage due to rehydration of the PIPOZ chain. A consequence of the adsorption hysteresis is that the friction forces measured at 25 °C are significantly lower after exposure to a temperature of 40 °C than prior to heating, which is due to higher polymer chain density on the surface after heating.
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| 2. |
- An, Junxue, et al.
(author)
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Comparison of a Brush-with-Anchor and a Train-of-Brushes Mucin on Poly(methyl methacrylate) Surfaces : Adsorption, Surface Forces, and Friction
- 2014
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In: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 15:4, s. 1515-1525
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Journal article (peer-reviewed)abstract
- Interfacial properties of two types of mucins have been investigated at the aqueous solution/poly(methyl methacrylate) (PMMA) interface. One is commercially available bovine submaxillary mucin, BSM, which consists of alternating glycosylated and nonglycosylated regions. The other one is a recombinant mucin-type fusion protein, PSGL-1/mIgG(2b), consisting of a glycosylated mucin part fused to the Fc part of an immunoglobulin. PSGL-1/mIgG(2b) is mainly expressed as a (timer upon production. A quartz crystal microbalance with dissipation was used to study the adsorption of the mucins to PMMA surfaces. The mass of the adsorbed mucin layers, including the adsorbed mucin and water trapped in the layer, was found to be significantly higher for PSGL-1/mIgG(2b) than for BSM. Atomic force microscopy with colloidal probe was employed to study interactions and frictional forces between mucin-coated PMMA surfaces. Purely repulsive forces of steric origin were Observed between PSGL-1/mIgG(2b) mucin layers, whereas a small adhesion was detected between BSM layers and attributed to bridging. Both mucin layers reduced the friction force between PMMA surfaces in aqueous solution. The reduction was, however, significantly more pronounced for PSGL-1/mIgG(2b). The effective friction coefficient between PSGL-1/mIgG(2b)-coated PMMA surfaces is as low as 0.02 at low loads, increasing to 0.24 at the highest load explored, 50 nN. In contrast, a friction coefficient of around 0.7 was obtained between BSM-coated PMMA surfaces. The large differences in interfacial properties for the two mucins are discussed in relation to their structural differences.
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| 3. |
- An, Junxue, et al.
(author)
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Influence of Glycosylation on Interfacial Properties of Recombinant Mucins : Adsorption, Surface Forces, and Friction
- 2017
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In: Langmuir. - : American Chemical Society. - 0743-7463 .- 1520-5827. ; 33:18, s. 4386-4395
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Journal article (peer-reviewed)abstract
- Interfacial properties of two brush-with-anchor mucins, C-P55 and C-PSLex, have been investigated at the aqueous solution/poly(methyl methacrylate) (PMMA) interface. Both are recombinant mucin-type fusion proteins, produced by fusing the glycosylated mucin part of P-selectin glycoprotein ligand-1 (PSLG-1) to the Fc part of a mouse immunoglobulin in two different cells. They are mainly expressed as dimers upon production. Analysis of the O-glycans shows that the C-PSLex mucin has the longer and more branched side chains, but C-P55 has slightly higher sialic acid content. The adsorption of the mucins to PMMA surfaces was studied by quartz crystal microbalance with dissipation. The sensed mass, including the adsorbed mucin and water trapped in the layer, was found to be similar for these two mucin layers. Atomic force microscopy with colloidal probe was employed to study surface and friction forces between mucin-coated PMMA surfaces. Purely repulsive forces of steric origin were observed between mucin layers on compression, whereas a small adhesion was detected between both mucin layers on decompression. This was attributed to chain entanglement. The friction force between C-PSLex-coated PMMA is lower than that between C-P55-coated PMMA at low loads, but vice versa at high loads. We discuss our results in terms of the differences in the glycosylation composition of these two mucins.
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| 4. |
- An, Junxue, et al.
(author)
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Influence of Glycosylation on Interfacial Properties of Recombinant Mucins: Adsorption, Surface Forces and Friction
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Other publication (other academic/artistic)abstract
- Interfacial properties of two brush-with-anchor mucins, C-P55 and C-PSLex, have been investigated at the aqueous solution/poly(methylmethacrylate) (PMMA) interface. Both are recombinant mucin-type fusion proteins, produced by fusing the glycosylated mucin part of P-selectin glycoprotein ligand-1 (PSLG-1) to the Fc part of a mouse immunoglobulin in two different cells. They are mainly expressed as dimers upon production. Analysis of the O-glycans shows that the C-PSLex mucin has the longer and more branched side chains, but C-P55 has slightly higher sialic acid content. The adsorption of the mucins to PMMA surfaces was studied by quartz crystal microbalance with dissipation. The sensed mass, including the adsorbed mucin and water trapped in the layer, was found to be similar for these two mucin layers. Atomic force microscopy with colloidal probe was employed to study surface and friction forces between mucin-coated PMMA surfaces. Purely repulsive forces of steric origin were observed between mucin layers on compression, whereas a small adhesion was detected between both mucin layers on decompression. This was attributed to chain entanglement. The friction force between C-PSLex-coated PMMA is lower than that between C-P55-coated PMMA at low loads, but vice versa at high loads. We discuss our results in terms of the differences in the glycosylation composition of these two mucins.
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| 5. |
- An, Junxue, et al.
(author)
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Temperature-Dependent Adsorption and Adsorption Hysteresis of a Thermoresponsive Diblock Copolymer
- 2014
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In: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 30:15, s. 4333-4341
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Journal article (peer-reviewed)abstract
- A nonionic-cationic diblock copolymer, poly(2-isopropyl-2-oxazoline)(60)-b-poly((3-acrylamidopropyl)- trimethylammonium chloride)(17), (PIPOZ(60)-b-PAMPTMA(17)), was utilized to electrostatically tether temperature-responsive PIPOZ chains to silica surfaces by physisorption. The effects of polymer concentration, pH, and temperature on adsorption were investigated using quartz crystal microbalance with dissipation monitoring and ellipsometry. The combination of these two techniques allows thorough characterization of the adsorbed layer in terms of surface excess, thickness, and water content. The high affinity of the cationic PAMPTMA(17) block to the negatively charged silica surface gives rise to a high affinity adsorption isotherm, leading to (nearly) irreversible adsorption with respect to dilution. An increase in solution pH lowers the affinity of PIPOZ to silica but enhances the adsorption of the cationic block due to increasing silica surface charge density, which leads to higher adsorption of the cationic diblock copolymer. Higher surface excess is also achieved at higher temperatures due to the worsening of the solvent quality of water for the PIPOZ block. Interestingly, a large hysteresis in adsorbed mass and other layer properties was observed when the temperature was cycled from 25 to 45 degrees C and then back to 25 degrees C. Possible causes for this temperature hysteresis are discussed.
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| 6. |
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| 7. |
- An, Junxue, et al.
(author)
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Tethered Poly(2-isopropyl-2-oxazoline) Chains : Temperature Effects on Layer Structure and Interactions Probed by AFM Experiments and Modeling
- 2015
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In: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 31:10, s. 3039-3048
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Journal article (peer-reviewed)abstract
- Thermoresponsive polymer layers on silica surfaces have been obtained by utilizing electrostatically driven adsorption of a cationic-nonionic diblock copolymer. The cationic block provides strong anchoring to the surface for the nonionic block of poly(2-isopropyl-2-oxazoline), referred to as PIPOZ. The PIPOZ chain interacts favorably with water at low temperatures, but above 46 degrees C aqueous solutions of PIPOZ phase separate as water becomes a poor solvent for the polymer. We explore how a change in solvent condition affects interactions between such adsorbed layers and report temperature effects on both normal forces and friction forces. To gain further insight, we utilize self-consistent lattice mean-field theory to follow how changes in temperature affect the polymer segment density distributions and to calculate surface force curves. We find that with worsening of the solvent condition an attraction develops between the adsorbed PIPOZ layers, and this observation is in good agreement with predictions of the mean-field theory. The modeling also demonstrates that the segment density profile and the degree of chain interpenetration under a given load between two PIPOZ-coated surfaces rise significantly with increasing temperature.
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| 8. |
- Bastardo Zambrano, Luis Alejandro, et al.
(author)
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Soluble complexes in aqueous mixtures of low charge density comb polyelectrolyte and oppositely charged surfactant probed by scattering and NMR
- 2007
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In: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 312, s. 21-33
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Journal article (peer-reviewed)abstract
- A low charge density polyelectrolyte with a high graft density of 45 units long poly(ethylene oxide) side-chains has been synthesized. In this comb polymer, denoted PEO45 MEMA:METAC-2, 2 mol% of the repeating methacrylate units in the polymer backbone carry a permanent positive charge and the remaining 98 mol% a 45 unit long PEO side-chain. Here we describe the solution conformation of this polymer and its association with an anionic surfactant, sodium dodecylsulfate, SDS. It will be shown that the polymer can be viewed as a stiff rod with a cross-section radius of gyration of 29 Å. The cross section of the rod contracts with increasing temperature due to decreased solvency of the PEO side-chains. The anionic surfactant associates to a significant degree with PEO45 MEMA:METAC-2 to form soluble complexes at all stoichiometries. A cooperative association is observed as the free SDS concentration approaches 7 mM. At saturation the number of SDS molecules associated with the polymer amounts to 10 for each PEO side-chain. Two distinct populations of associated surfactants are observed, one is suggested to be molecularly distributed over the comb polymer and the other constitutes small micellar-like structures at the periphery of the aggregate. These conclusions are reached based on results from small-angle neutron scattering, static light scattering, NMR, and surface tension measurements.
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| 9. |
- Beldowski, Piotr, et al.
(author)
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Albumin-Hyaluronan Interactions : Influence of Ionic Composition Probed by Molecular Dynamics
- 2021
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In: International Journal of Molecular Sciences. - : MDPI AG. - 1661-6596 .- 1422-0067. ; 22:22
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Journal article (peer-reviewed)abstract
- The lubrication mechanism in synovial fluid and joints is not yet fully understood. Nevertheless, intermolecular interactions between various neutral and ionic species including large macromolecular systems and simple inorganic ions are the key to understanding the excellent lubrication performance. An important tool for characterizing the intermolecular forces and their structural consequences is molecular dynamics. Albumin is one of the major components in synovial fluid. Its electrostatic properties, including the ability to form molecular complexes, are closely related to pH, solvation, and the presence of ions. In the context of synovial fluid, it is relevant to describe the possible interactions between albumin and hyaluronate, taking into account solution composition effects. In this study, the influence of Na+, Mg2+, and Ca2+ ions on human serum albumin-hyaluronan interactions were examined using molecular dynamics tools. It was established that the presence of divalent cations, and especially Ca2+, contributes mostly to the increase of the affinity between hyaluronan and albumin, which is associated with charge compensation in negatively charged hyaluronan and albumin. Furthermore, the most probable binding sites were structurally and energetically characterized. The indicated moieties exhibit a locally positive charge which enables hyaluronate binding (direct and water mediated).
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| 10. |
- Bełdowski, Piotr, et al.
(author)
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Collagen type II-hyaluronan interactions - the effect of proline hydroxylation: a molecular dynamics study
- 2022
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In: Journal of materials chemistry. B. - : Royal Society of Chemistry. - 2050-750X .- 2050-7518. ; 10:46, s. 9713-9723
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Journal article (peer-reviewed)abstract
- Hyaluronan-collagen composites have been employed in numerous biomedical applications. Understanding the interactions between hyaluronan and collagen is particularly important in the context of joint cartilage function and the treatment of joint diseases. Many factors affect the affinity of collagen for hyaluronan. One of the important factors is the ratio of 3- or 4-hydroxy proline to proline residues. This article presents the results from molecular dynamics calculations of HA-collagen type II interactions with hyaluronan. The applied protocol employed docking and geometry optimization of complexes built using collagen structures with different numbers of hydroxyl groups attached to proline moieties. It was established that the hydroxyproline/proline ratio affects both structural and energetic features of the collagen-hyaluronan complex. Proline hydroxylation was found to significantly influence the number of all identified types of molecular forces, hydrophobic interactions, water bridges and hydrogen bonds, which can be formed between collagen and hyaluronan. Importantly, an increase in the hydroxyproline/proline ratio in the collagen chain increases the binding affinity for hyaluronan. This is illustrated by the linear correlation between the binding free energy and the hydroxylation degree. A comparison of the results obtained for 3 and 4 hydroxylation of proline indicates that the hydroxyl group attachment position plays a minor role in complex stabilization. However, a slightly stronger affinity was observed for 4 hydroxylation. In order to evaluate the effect of the aqueous environment on the collagen-hyaluronan complex stability, the enthalpic and entropic contributions to the free energy of solvation were analyzed.
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