| 1. |
- Alves, Luis, et al.
(författare)
-
On the role of hydrophobic interactions in cellulose dissolution and regeneration: Colloidal aggregates and molecular solutions
- 2015
-
Ingår i: Colloids and Surfaces A: Physicochemical and Engineering Aspects. - : Elsevier BV. - 0927-7757. ; 483, s. 257-263
-
Tidskriftsartikel (refereegranskat)abstract
- The development of strategies for dissolution and regeneration of cellulose constitutes an increasingly active research field due to the direct relevance for many production processes and applications. A wide variety of suitable solvents for cellulose are already available. However, cellulose solvents are of highly different nature reflecting the great challenges in the understanding of the subtle balance between the different interactions. Here, we report on the effect of two different solvents on the dissolution of cellulose on multiple length scales and its consequences for the characteristics of the regenerated material. While an aqueous tetrabutylammonium hydroxide solution gives rise to what appears to be dissolution down to the molecular level, a sodium hydroxide solution does not dissolve cellulose molecularly but rather leaves aggregates of high crystallinity stable in the cellulose dope. The dramatic difference between a small inorganic cation and an amphiphilic cation indicates a critical role of hydrophobic interactions between cellulose molecules and provides support for the picture that cellulose molecules have pronounced amphiphilic properties. (C) 2015 Elsevier B.V. All rights reserved.
|
|
| 2. |
- Antunes, Filipe, et al.
(författare)
-
A rheological investigation of the association between a non-ionic microemulsion and hydrophobically modified PEG. Influence of polymer architecture
- 2003
-
Ingår i: Colloids and Surfaces A: Physicochemical and Engineering Aspects. - 0927-7757. ; 215:1-3, s. 87-100
-
Tidskriftsartikel (refereegranskat)abstract
- ydrophobically modified polymers (HM-P) typically behave as thickeners in a wide range of systems. The thickening effect in an aqueous solution of this kind of polymer depends on intermolecular hydrophobic associations and also on chain entanglements if the polymer concentration is significantly above the overlap concentration. In the present investigation a rather short end-capped polymer has been investigated at concentrations that are significantly below the overlap concentration. Despite the rather low polymer concentration, polymer chains were connected into a three-dimensional network by using microemulsion droplets as cross-linking points. The simple structure of the solution simplifies interpretations of results since chain entanglements can be expected to be of low importance and only intermolecular hydrophobic associations have to be considered. In particular the rheological response is in most cases well characterized by one single relaxation time and, then, the solution can be rationalized withi the framework of the Maxwell model. We have found that the length of the polymer chain's hydrophobic end-groups, as well as the temperature, have a large influence on dynamics of the system, while the length of the hydrophilic mid-block has a relatively small significance. On the other hand, the connectivity in the system depends critically on the microemulsion concentration. Thus, a maximum was found in viscosity as a function of volume fraction, interpreted as being due to a decrease in crosslink lifetime. (C) 2002 Elsevier Science B.V. All rights reserved.
|
|
| 3. |
- Antunes, Filipe E., et al.
(författare)
-
Polymer-vesicle association
- 2009
-
Ingår i: Advances in Colloid and Interface Science. - : Elsevier BV. - 1873-3727 .- 0001-8686. ; 147-48, s. 18-35
-
Forskningsöversikt (refereegranskat)abstract
- Mixed polymer-surfactant systems have been intensively investigated in the last two decades, with the main focus on surfactant micelles as the surfactant aggregate in interaction. The main types of phase behavior, driving forces and structural/rheological effects at stake are now fairly well understood. Polymer-vesicle systems, on the other hand, have received comparatively less attention from a physico-chemical perspective. In this review, our main goal has been to bridge this gap, taking a broad approach to cover a field that is in clear expansion, in view of its multiple implications for colloid and biological sciences and in applied areas. We start by a general background on amphiphile self-assembly and phase separation phenomena in mixed polymer-surfactant solutions. We then address vesicle formation, properties and stability not only in classic lipids, but also in various other surfactant systems, among which catanionic vesicles are highlighted. Traditionally. lipid and surfactant vesicles have been studied separately, with little cross-information and comparison, giving duplication of physico-chemical interpretations. This situation has changed in more recent times. We then proceed to cover more in-depth the work done on different aspects of the associative behavior between vesicles (of different composition and type of stability) and different types of polymers, including polysaccharides. proteins and DNA. Thus. phase behavior features. effects of vesicle structure and stability, and the forces/mechanisms of vesicle-macromolecule interaction are addressed. Such association may generate gels with interesting theological properties and high potential for applications. Finally, special focus is also given to DNA, a high charge polymer. and its interactions with surfactants, and vesicles. in particular, in the context of gene transfection studies. (C) 2008 Elsevier B.V. All rights reserved
|
|
| 4. |
- Antunes, Filipe, et al.
(författare)
-
Mechanisms behind the faceting of catanionic vesicles by polycations: Chain crystallization and segregation
- 2007
-
Ingår i: The Journal of Physical Chemistry Part B. - 1520-5207. ; 111:1, s. 116-123
-
Tidskriftsartikel (refereegranskat)abstract
- Vesicles composed of an anionic and a cationic surfactant, with a net negative charge, associate strongly with a hydrophobically modified polycation (LM200) and with an unmodified polycation with higher charge density (JR400), forming viscoelastic gel-like structures. Calorimetric results show that in these gels, LM200 induces a rise of the chain melting temperature (T-m) of the vesicles, whereas JR400 has the opposite effect. For both polymer-vesicle systems, the shear viscosity exhibits an inflection point at T-m, and for the LM200 system the measured relaxation times are significantly higher below T-m. The neat vesicles and the polycation-bound vesicles have a polygonal-like faceted shape when the surfactant chains in the bilayer are crystallized, as probed by cryo-transmission electron microscopy. Above T-m, the neat and the LM200-bound vesicles regain a spheroidal shape, whereas those in the JR400 system remain with a deformed faceted shape even above T-m. These shape changes are interpreted in terms of different mechanisms for the polymer-vesicle interaction, which seem to be highly dependent on polymer architecture, namely charge density and hydrophobic modification. A crystallization-segregation mechanism is proposed for the LM200-vesicle system, while, for the JR400-vesicle one, charge polarization-lateral segregation effects induced by the polycation in the catanionic bilayer are envisaged.
|
|
| 5. |
- Antunes, Filipe, et al.
(författare)
-
Mixed systems of hydrophobically modified polyelectrolytes: Controlling rheology by charge and hydrophobe stoichiometry and interaction strength
- 2005
-
Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 21:22, s. 10188-10196
-
Tidskriftsartikel (refereegranskat)abstract
- Rheology and phase separation were investigated for aqueous mixtures of two oppositely charged hydrophobically modified polyelectrolytes. The typical phase separation, normally seen for oppositely charged polymer mixtures, is dramatically reduced by the presence of hydrophobic modification, and phase separation is only detected close to the point of charge neutralization. While the two polyelectrolytes separately can give high viscosities and a gel-like behavior, a pronounced maximum in viscosity and storage modulus with the mixing ratio of the polyelectrolytes is observed; the maximum is located between the points of charge and hydrophobe stoichiometry and reflects a combination of hydrophobic and electrostatic association. Lowering the charge density of the anionic polymer leads to a strengthened association at first, but at lower charge densities there is a weakened association due to the onset of phase separation. The strength of the electrostatic interaction was modified by adding salt. Increased ionic strength can lead to phase separation and to increased or decreased viscosity depending on the polyelectrolyte mixing ratio.
|
|
| 6. |
- Antunes, Filipe, et al.
(författare)
-
Network formation of catanionic vesicles and oppositely charged polyelectrolytes. Effect of polymer charge density and hydrophobic modification
- 2004
-
Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 20:11, s. 4647-4656
-
Tidskriftsartikel (refereegranskat)abstract
- In nonequimolar solutions of a cationic and an anionic surfactant, vesicles bearing a net charge can be spontaneously formed and apparently exist as thermodynamically stable aggregates. These vesicles can associate strongly with polymers in solution by means of hydrophobic and/or electrostatic interactions. In the current work, we have investigated the rheological and microstructural properties of mixtures of cationic polyelectrolytes and net anionic sodium dodecyl sulfate/didodecyldimethylammonium bromide vesicles. The polyelectrolytes consist of two cationic cellulose derivatives with different charge densities; the lowest charge density polymer contains also hydrophobic grafts, with the number of charges equal to the number of grafts. For both systems, polymer-vesicle association leads to a major increase in viscosity and to gel-like behavior, but the viscosity effects are more pronounced for the less charged, hydrophobically modified polymer. Evaluation of the frequency dependence of the storage and loss moduli for the two systems shows further differences in behavior: while the more long-lived cross-links occur for the more highly charged hydrophilic polymer, the number of cross-links is higher for the hydrophobically modified polymer. Microstructure studies by cryogenic transmission electron microscopy indicate that the two polymers affect the vesicle stability in different ways. With the hydrophobically modified polymer, the aggregates remain largely in the form of globular vesicles and faceted vesicles (polygon-shaped vesicles with largely planar regions). For the hydrophilic polycation, on the other hand, the surfactant aggregate structure is more extensively modified: first, the vesicles change from a globular to a faceted shape; second, there is opening of the bilayers leading to holey vesicles and ultimately to considerable vesicle disruption leading to planar bilayer, disklike aggregates. The faceted shape is tentatively attributed to a crystallization of the surfactant film in the vesicles. It is inferred that a hydrophobically modified polyion with relatively low charge density can better stabilize vesicles due to formation of molecularly mixed aggregates, while a hydrophilic polyion with relatively high charge density associates so strongly to the surfactant films, due to strong electrostatic interactions, that the vesicles are more perturbed and even disrupted.
|
|
| 7. |
|
|
| 8. |
- Berezhnoy, Nikolay V., et al.
(författare)
-
Supramolecular Organization in Self-Assembly of Chromatin and Cationic Lipid Bilayers is Controlled by Membrane Charge Density
- 2012
-
Ingår i: Biomacromolecules. - : American Chemical Society (ACS). - 1526-4602 .- 1525-7797. ; 13:12, s. 4146-4157
-
Tidskriftsartikel (refereegranskat)abstract
- In this work we have investigated the structures of aggregates formed in model systems of dilute aqueous mixtures of "model chromatin" consisting of either recombinant nucleosome core particles (NCPs) or nucleosome arrays consisting of 12 NCPs connected with 30 bp linker DNA, and liposomes made from different mixtures of cationic and zwitterionic lipids, 1,2-dioleoyl-3-trimethylammonium-propane chloride salt (DOTAP) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The aggregates formed were characterized using different optical microscopy methods and small-angle X-ray scattering (SAXS), and the results are discussed in terms of the competing intermolecular interactions among the components. For a majority of the samples, the presence of lamellar structures could be identified. Ir. samples with high fractions of DOTAP in the liposomes, well-defined lamellar structures very similar to those formed by the corresponding lipid mixtures and DNA alone (i.e., without histone proteins) were observed; in these aggregates, the histones are expelled from the model chromatin. The findings suggest that, with liposomes containing large fractions of cationic lipid, the dominating driving force for aggregation is the increase in translational entropy from the release of counterions, whereas with lower fractions of the cationic lipid, the entropy of mixing of the lipids within the bilayers results in a decreased DNA-lipid attraction.
|
|
| 9. |
|
|
| 10. |
- Costa, Diana, et al.
(författare)
-
Effect of additives on swelling of covalent DNA gels
- 2007
-
Ingår i: The Journal of Physical Chemistry Part B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 111:29, s. 8444-8452
-
Tidskriftsartikel (refereegranskat)abstract
- The volumetric response of polymer gels on cosolute addition depends on the interaction of the polymer with the cosolute and can be used as a simple and sensitive way of elucidating these interactions. Here we report on DNA networks, prepared by crosslinking double-stranded DNA with ethylene glycol diglycidyl ether (EGDE); these have been investigated with respect to their swelling in aqueous solution containing different additives, such as metal ions, polyamines, charged proteins, and surfactants. The deswelling on addition of metal ions occurs at lower concentrations with increasing valency of the counterion. The collapse of the gels in the presence of trivalent ions seems to follow the same kind of mechanism as the interaction in solution, but addition of these ions leads to DNA denaturation and formation of single-stranded DNA. Striking features were found in the deswelling of DNA gels by chitosan, spermine, spermidine, lysozyme, poly-L-lysine and poly-L-arginine. Chitosan is the most efficient cosolute of those investigated with respect to DNA gel collapse. The effect of the cationic surfactant tail length on the volume phase transition of DNA gels was studied as a function of surfactant concentration. Cationic surfactants effectively collapsed the gel from the critical aggregation concentration (cac), decreasing with increasing length of the hydrophobic tail. In several cases, the deswelling as a function of cosolute concentration shows a pronounced two-step behavior, which is interpreted in terms of a combination of DNA chain condensation and general osmotic deswelling. The studies included investigations on the state of the DNA chain after deswelling, on the reversibility of the deswelling as well as on the kinetics. With the exception for the trivalent lanthanide ions, it appears that the DNA chain always retains a double-helix conformation; with these metal ions, single-stranded DNA is found. The deswelling appears to be reversible as exemplified by addition of anionic surfactant subsequent to gel collapsed by cationic surfactant and addition of sodium bromide to gels collapsed by a polycation. An investigation of the kinetics shows that an increase in the surfactant tail length gives a pronouncedly slower deswelling kinetics.
|
|
