| 1. |
- Kaspersen, Jørn D., et al.
(författare)
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Generic structures of cytotoxic liprotides : nano-sized complexes with oleic acid cores and shells of disordered proteins
- 2014
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Ingår i: ChemBioChem. - : Wiley-VCH Verlagsgesellschaft. - 1439-4227 .- 1439-7633. ; 15:18, s. 2693-2702
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Tidskriftsartikel (refereegranskat)abstract
- The cytotoxic complex formed between alpha-lactalbumin and oleic acid (OA) has inspired many studies on protein-fatty acid complexes, but structural insight remains sparse. After having used small-angle X-ray scattering (SAXS) to obtain structural information, we present a new, generic structural model of cytotoxic protein-oleic acid complexes, which we have termed liprotides (lipids and partially denatured proteins). Twelve liprotides formed from seven structurally unrelated proteins and prepared by different procedures all displayed core-shell structures, each with a micellar OA core and a shell consisting of flexible, partially unfolded protein, which stabilizes the OA micelle. The common structure explains similar effects exerted on cells by different liprotides and is consistent with a cargo off-loading of the OA into cell membranes.
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| 2. |
- Abelein, Axel, et al.
(författare)
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Formation of dynamic soluble surfactant-induced amyloid β peptide aggregation intermediates
- 2013
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Ingår i: Journal of Biological Chemistry. - 0021-9258 .- 1083-351X. ; 288:32, s. 23518-23528
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Tidskriftsartikel (refereegranskat)abstract
- Intermediate amyloidogenic states along the amyloid β peptide (Aβ) aggregation pathway have been shown to be linked to neurotoxicity. To shed more light on the different structures that may arise during Aβ aggregation, we here investigate surfactant-induced Aβ aggregation. This process leads to co-aggregates featuring a β-structure motif that is characteristic for mature amyloid-like structures. Surfactants induce secondary structure in Aβ in a concentration-dependent manner, from predominantly random coil at low surfactant concentration, via β-structure to the fully formed α-helical state at high surfactant concentration. The β-rich state is the most aggregation-prone as monitored by thioflavin T fluorescence. Small angle x-ray scattering reveals initial globular structures of surfactant-Aβ co-aggregated oligomers and formation of elongated fibrils during a slow aggregation process. Alongside this slow (minutes to hours time scale) fibrillation process, much faster dynamic exchange (k(ex) ∼1100 s(-1)) takes place between free and co-aggregate-bound peptide. The two hydrophobic segments of the peptide are directly involved in the chemical exchange and interact with the hydrophobic part of the co-aggregates. Our findings suggest a model for surfactant-induced aggregation where free peptide and surfactant initially co-aggregate to dynamic globular oligomers and eventually form elongated fibrils. When interacting with β-structure promoting substances, such as surfactants, Aβ is kinetically driven toward an aggregation-prone state.
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| 3. |
- Akesson, Anna, et al.
(författare)
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The effect of PAMAM G6 dendrimers on the structure of lipid vesicles
- 2010
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 12:38, s. 12267-12272
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Tidskriftsartikel (refereegranskat)abstract
- Dendrimers are polymers with unique properties that make them promising in a variety of applications such as potential drug and gene delivery systems. PAMAM dendrimers, in particular, have been widely investigated and are efficiently translocated into the cell. The mechanism of translocation, however, is still unknown. Recently it was proposed that PAMAM dendrimers are able to open holes in lipid bilayers by stealing lipid from the bilayer and forming "dendrisomes''. The present work intends to contribute in the clarification of this question: why are dendrimers able to translocate into the cell? We create simple models for cell membranes by using small lipid vesicles that present a single lipid phase at physiologically relevant conditions. We then follow the effect that dendrimers have on the structure of the vesicles by using a combination of various techniques: dynamic light scattering, cryo-TEM and small angle X-ray scattering. We discuss our results with respect to the previous findings and reflect on their possible implications for real translocation in living cells.
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| 4. |
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| 5. |
- Behrens, Manja A, et al.
(författare)
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Temperature-Induced Attractive Interactions of PEO-Containing Block Copolymer Micelles
- 2014
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 30:21, s. 6021-6029
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Tidskriftsartikel (refereegranskat)abstract
- Interactions in a temperature sensitive-colloidal model system are investigated over a wide range of temperatures and concentrations to characterize the interparticle interactions within the system. This model system is composed of poly(ethylene oxide) end-capped with an octadecyl chain (C18E100), which by small-angle X-ray scattering (SAXS) have been shown to form spherical micelles in an aqueous salt solution. In the present study a 0.9 M NaF solution is used to shift the cloud point into the experimentally convenient temperature range. Densitometry and SAXS have shown no indication of specific interactions between the salt ions and the micelles. The spherical micelles are found to persist at elevated temperatures and a change in interparticle interaction is observed by viscometry and SAXS. The results are all consistent with the decreased solvent quality of water toward poly(ethylene oxide) with increasing temperature and it is seen that attractive interparticle interactions emerge in the vicinity of the cloud point.
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| 6. |
- Bergström, L. Magnus, et al.
(författare)
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The growth of micelles, and the transition to bilayers, in mixtures of a single-chain and a double-chain cationic surfactant investigated with small-angle neutron scattering
- 2011
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Ingår i: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-683X .- 1744-6848. ; 7:22, s. 10935-10944
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Tidskriftsartikel (refereegranskat)abstract
- Self-assembly in aqueous mixtures of a single-chain (DTAB) and a double-chain cationic surfactant (DDAB) has been investigated with small-angle neutron scattering (SANS). Small oblate spheroidal micelles formed by DTAB grow with respect to width and length to form mixed ellipsoidal tablet-shaped micelles as an increasing fraction of DDAB is admixed into the micelles. The growth behaviour of the micelles is rationalized from the general micelle model in terms of three bending elasticity constants spontaneous curvature (H-0), bending rigidity (k(c)) and saddle-splay constant ((k(c)) over bar kc). It is found that micelles grow with respect to width, mainly as a result of decreasing k(c)H(0), and in the length direction as a result of decreasing k(c). The micelles are still rather small, i.e. about 140 angstrom in length, as an abrupt transition to large bilayer aggregates is observed. The micelle-to-bilayer transition is induced by changes in aggregate composition and is observed to occur at a mole fraction of DDAB equal to about x = 0.48 in D2O, which is a significantly higher value than previously observed for the same system in H2O (x = 0.41). An abrupt micelle-to-bilayer transition is in agreement with predictions from the general micelle model, according to which an abrupt transition from micelles to bilayers is expected to occur at xi H-0 = 1/4, where x is the thickness of the self-assembled interface, and we may conclude that H-0(D2O) > H-0(H2O) for the system DDAB/DTAB in absence of added salt. Samples with bilayers are found to be composed of bilayer disks coexisting with vesicles. Disks are found to always predominate over vesicles with mass fractions about 70-90% disks and 10-30% vesicles. Micelles, disks and vesicles are observed to coexist in a few samples close to the micelle-to-bilayer transition.
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| 7. |
- Bodvik, Rasmus, et al.
(författare)
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Aggregation and network formation of aqueous methylcellulose and hydroxypropylmethylcellulose solutions.
- 2010
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Ingår i: Colloids and Surfaces A. - : Elsevier. - 0927-7757 .- 1873-4359. ; 354:1-3, s. 162-171
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Tidskriftsartikel (refereegranskat)abstract
- Solution properties of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) have been investigated as a function of temperature and concentration using a broad range of experimental techniques. Novelties include the extensive comparison between MC and HPMC solutions as well as the combination of techniques, and the use of Cryo transmission electron microscopy (Cryo-TEM). The correlation between rheology and light scattering results clearly demonstrates the relation between viscosity change and aggregation. Cryo-TEM images show the network structures formed. Viscosity measurements show that for both MC and HPMC solutions sudden changes in viscosity occur as the temperature is increased. The onset temperature for these changes depends on polymer concentration and heating rate. For both MC and HPMC solutions the viscosity on cooling is very different compared to on heating, demonstrating the slow equilibration time. The viscosity changes in MC and HPMC solutions are dramatically different; for MC solutions the viscosity increases by several orders of magnitude when a critical temperature is reached, whereas for HPMC solutions the viscosity decreases abruptly at a given temperature, followed by an increase upon further heating. Light and (SAXS) small-angle X-ray scattering shows that the increase in viscosity, for MC as well as for HPMC solutions, is due to extensive aggregation of the polymers. Light scattering also provides information on aggregation kinetics. The SAXS measurements allow us to correlate aggregation hysteresis to the viscosity hysteresis, as well as to extract some structural information. Cryo-TEM images give novel information that a fibrillar network is formed in MC solutions, and the strong viscosity increase occurs when this network spans the whole solution volume. For HPMC solutions the behaviour is more complex. The decrease in viscosity can be related to the formation of compact objects, and the subsequent increase to formation of fibrillar structures, which are more linear and less entangled than for MC.
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| 8. |
- Gibaud, Thomas, et al.
(författare)
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New routes to food gels and glasses
- 2012
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Ingår i: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498 .- 1359-6640. ; 158, s. 267-284
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Tidskriftsartikel (refereegranskat)abstract
- We describe the possibility to create solid-like protein samples whose structural and mechanical properties can be varied and tailored over an extremely large range in a very controlled way through an arrested spinodal decomposition process. We use aqueous lysozyme solutions as a model globular protein system. A combination of video microscopy, small-angle neutron and X-ray scattering and reverse Monte Carlo modeling is used to characterize the structure of the bicontinuous network with two coexisting phases of a dilute protein solution and a glassy or arrested dense protein backbone at all relevant length scales. Rheological measurements are then used to determine the complex mechanical response of these protein gels as a function of protein concentration and quench temperature. While in particular the origin of the dependence of the mechanical properties on quench depth and concentration is not well understood currently, it seems ultimately connected to the particular bicontinuous structure of the arrested spinodal network created by the interplay between the early stage of a spinodal decomposition and the position of the glass line. We then generalize this behavior and discuss how this could open up new routes to prepare gel-like food systems with adjustable structural and mechanical properties. We present results from a first feasibility study where we use a depletion interaction caused by the addition of small non-adsorbing polymers to suspensions of casein micelles in order to create food gels with tunable structural and mechanical properties through an arrested spinodal decomposition process.
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| 9. |
- Madenci, Dilek, et al.
(författare)
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Simple model for the growth behaviour of mixed lecithin-bile salt micelles
- 2011
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084. ; 13:8, s. 3171-3178
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Tidskriftsartikel (refereegranskat)abstract
- Mixed lecithin-bile salt micelles are known to have a cylindrical or worm-like structure. We investigated their shape, length, flexibility and cross-sectional structure using small-angle neutron scattering (SANS). A broad range of sample compositions was studied varying both the total amphiphile concentration and the molar ratio of bile salt (sodium taurochenodeoxycholate, NaTCDC) to lecithin (egg yolk phosphatidylcholine, EYL). The length of the micelles was quantitatively linked to the micellar composition by introducing a simple model. The model takes into account the partitioning of lecithin and bile salt between the bulk, cylindrical parts and the end caps of the micelles. The model also sheds light on the organization of the micelles, both in their cylindrical regions and end caps.
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| 10. |
- Sharifi, Soheil, et al.
(författare)
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Variations in Structure Explain the Viscometric Behavior of AOT Microemulsions at Low Water/AOT Molar Ratios
- 2012
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Ingår i: Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics. - : Walter de Gruyter GmbH. - 0942-9352. ; 226:3, s. 201-218
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Tidskriftsartikel (refereegranskat)abstract
- The viscosity of AOT/water/decane water-in-oil microemulsions exhibits a well-known maximum as a function of water/AOT molar ratio, which is usually attributed to increased attractions among nearly spherical droplets. The maximum can be removed by adding salt or by changing the oil to CCl4. Systematic small-angle X-ray scattering (SAXS) measurements have been used to monitor the structure of the microemulsion droplets in the composition regime where the maximum appears. On increasing the droplet concentration, the scattering intensity is found to scale with the inverse of the wavevector, a behavior which is consistent with cylindrical structures. The inverse wavevector scaling is not observed when the molar ratio is changed, moving the system away from the value corresponding to the viscosity maximum. It is also not present in the scattering from systems containing enough added salt to essentially eliminate the viscosity maximum. An asymptotic analysis of the SAXS data, complemented by some quantitative modeling, is consistent with cylindrical growth of droplets as their concentration is increased. Such elongated structures are familiar from related AOT systems in which the sodium counterion has been exchanged for a divalent one. However, the results of this study suggest that the formation of non-spherical aggregates at low molar ratios is an intrinsic property of AOT.
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| 11. |
- Tyrsted, Christoffer, et al.
(författare)
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In-Situ Synchrotron Radiation Study of Formation and Growth of Crystalline CexZr1-xO2 Nanoparticles Synthesized in Supercritical Water
- 2010
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 22:5, s. 1814-1820
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Tidskriftsartikel (refereegranskat)abstract
- In situ synchrotron powder X-ray diffraction (PXRD) measurements have been conducted to follow the nucleation and growth of crystalline CexZr1-xO2 nanoparticles synthesized in supercritical water with a full substitution variation (x = 0, 0.2, 0.5, 0.8, and 1.0). Direction-dependent growth curves are determined and described using reaction kinetic models. A disctinct change in growth kinetics is observed with increasing cerium content. For x = 0.8 and 1.0 (high cerium content), the growth in initially limited by the surface reaction kinetics, however, at a size of similar to 6 nm, the growth changes and becomes limited by the diffusion of monomers toward the surface. For x = 0 and 0.2, the opposite behavior is observed with the growth initially being limited by diffusion (up to similar to 3.5 nm) and later by the surface reaction kinetics. Thus, although a continuous solid solution can be obtained for the ceria-zirconia system, the growth of ceria and zirconia nanoparticles is fundamentally different under supercritical flow reactor. The resulting samples were analyzed using PXRD, small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). The nanoparticles with x = 0, 0.2, and 0.5 have very low polydispersities. The sizes range from 4 nm to 7 nm, and the particles exhibit a reversibly pH-dependent agglomeration.
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