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Polyelectrolyte complexes of bottle brush copolymers: Solution and adsorption properties
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The aim of this thesis work was to systematically investigate the physico-chemical properties of polyelectrolyte complexes (PECs) formed by bottle brush and linear polyelectrolytes in solution and at solid / liquid interfaces. Electrostatic self-assembly of oppositely charged macromolecules in aqueous solution is a versatile strategy to construction of functional nanostructures with easily controlled properties. Bottle brush architecture, introduced into the PEC, generates a number of distinctive properties of the complexes, related to a broad range of application, such as colloidal stability and protein repellency to name a few. To utilize these materials in a wide range of applications e.g. drug delivery, the understanding of the effects of polymer architecture and solution parameters on the properties of bottle brush PECs is of paramount importance. This thesis constitutes a systematic investigation of PECs formed by a series of cationic bottle-brush polyelectrolytes and a series of anionic linear polyelectrolytes in aqueous solution. The focus of the first part of the thesis was primarily on formation and characterization of PECs in solution, whereas the adsorption properties and adsorption kinetics of bottle-brush polyelectrolytes and their complexes was investigated in the second part of the thesis work. In particular, effects of the side-chain density of the bottlebrush polyelectrolyte, concentration, mixing ratio and molecular weigh of the linearpolyelectrolyte on formation, solution properties, stability and adsorption of PECs were addressed.

The pronounced effect of the side-chain density of the bottle-brush polyelectrolyte on the properties of stoichiometric and nonstoichiometric PECs was demonstrated. Formation of PECs by bottle-brush copolymers with high density of side-chains results in small, watersoluble, molecular complexes having nonspherical shape, independent of concentration. Whereas formation of PEC-aggregates was revealed by bottle-brush polyelectrolytes with low side chain density, the level of aggregation in these complexes is controlled by polyelectrolyte concentration. The structure of the PECs formed with low molecular weight polyanions is consistent with the picture that several small linear polyelectrolyte molecules associate with the large bottle-brush. In contrast, when complexation occurs between polyanions of high molecular weigh and the bottle-brush polymers considerably larger PECs are formed, consistent with several bottle-brush polymers associating with one high molecular weight polyanion.

Place, publisher, year, edition, pages
Stockholm: KTH-Royal Institute of Technology , 2011. , xiii, 62 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:37
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-33666ISBN: 978-91-7415-998-1OAI: oai:DiVA.org:kth-33666DiVA: diva2:416959
Public defence
2011-06-01, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (Swedish)
Opponent
Supervisors
Funder
Swedish Research Council
Note
QC 20110516Available from: 2011-05-16 Created: 2011-05-13 Last updated: 2012-03-12Bibliographically approved
List of papers
1. Formation and Stability of Soluble Stochiometric Polyelectrolyte Complexes: Effects of Charge Density and Polyelectrolyte Concentration
Open this publication in new window or tab >>Formation and Stability of Soluble Stochiometric Polyelectrolyte Complexes: Effects of Charge Density and Polyelectrolyte Concentration
2009 (English)In: Journal of Dispersion Science and Technology, ISSN 0193-2691, E-ISSN 1532-2351, Vol. 30, no 6, 980-988 p.Article in journal (Refereed) Published
Abstract [en]

Sterically stabilized polyelectrolyte complexes with stoichiometric composition between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights have been prepared. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion and a range of brush copolymers with various molar ratio (X=1, 0.75, 0.5, 0.25) of the poly-methacryloxyethyl trimethylammonium chloride poly(METAC) and the nonionic poly(ethylene oxide) methyl ether methacrylate poly(PEO45MEMA) were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration and charge density of the cationic polyelectrolyte. The data obtained suggest that the PEO45- rich systems, NaPSS/PEO45MEMA:METAC-25 and NaPSS/PEO45MEMA:METAC-50, form small, water-soluble, molecular complexes having nonspherical shape. The PEO45-poor NaPSS/PEG45MEMA:METAC-75 form turbid colloidal dispersions, whereas insoluble PECs were revealed for the PEO45-free NaPSS/METAC system. The aggregation level of the PEO45-poor systems is mainly controlled by the concentration of the component solutions used for the preparation of PECs, whereas the aggregation of PEO45-rich nanoparticles is prevented by means of steric stabilization. Electrophoretic mobility data indicate a close to charge neutral state of the generated polyelectrolyte complexes.

Identifiers
urn:nbn:se:kth:diva-18459 (URN)10.1080/01932690802646512 (DOI)000266436200029 ()2-s2.0-70449435311 (ScopusID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2011-05-16Bibliographically approved
2. Formation and Stability of Water-Soluble Molecular Polyelectrolyte Complexes: Effects of Charge Density, Mixing Ratio and Polyelectrolyte Concentration
Open this publication in new window or tab >>Formation and Stability of Water-Soluble Molecular Polyelectrolyte Complexes: Effects of Charge Density, Mixing Ratio and Polyelectrolyte Concentration
2009 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 25, no 11, 6113-6121 p.Article in journal (Refereed) Published
Abstract [en]

The formation of complexes with stoichiometric (1:1) as well as nonstoichiometric (2:1) and (1:2) compositions between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights is reported in this contribution. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion, and a range of copolymers with various molar ratios of the poly(methacryloxyethyltrimethylammonium) chloride, poly(METAC), and the nonionic poly(ethylene oxide) ether methacrylate, poly(PEO45MEMA), were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity, and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration, charge density of the cationic polyelectrolyte, and mixing ratio. The data obtained demonstrate that in the absence of PEO45 side chains the 100% charged polymer (polyMETAC) formed insoluble PECs with PSS that precipitate from solution when exact stoichiometry is achieved. In nonstoichiometric complexes (1:2) and (2:1) large colloidally stable aggregates were formed. The presence of even a relatively small amount of PEO45 side chains (25%) in the cationic copolymer was sufficient for preventing precipitation of the formed stoichiometric and nonstoichiometric complexes. These PEC’s are sterically stabilized by the PEO45 chains. By further increasing the PEO45 side-chain content (50 and 75%) of the cationic copolymer, small, water-soluble molecular complexes could be formed. The data suggest that PSS molecules and the charged backbone of the cationic brush form a compact core, and with sufficiently high PEO45 chain density (above 25%) molecular complexes are formed that are stable over prolonged times.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2009
Keyword
ENTRAPPING ENZYME MOLECULES; DILUTE AQUEOUS-SOLUTION; SALT CONCENTRATION; BLOCK-COPOLYMERS; CHAIN-LENGTH; MICELLES; DELIVERY; POLYCATIONS; SCATTERING; GLYCOL
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-70251 (URN)000266604000020 ()2-s2.0-66749184130 (ScopusID)
Note
QC 20120207Available from: 2012-02-07 Created: 2012-01-30 Last updated: 2012-03-12Bibliographically approved
3. Adsorption characteristics of brush polyelectrolytes on silicon oxynitride revealed by dual polarisation interferometry
Open this publication in new window or tab >>Adsorption characteristics of brush polyelectrolytes on silicon oxynitride revealed by dual polarisation interferometry
Show others...
2010 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 348, 189-197 p.Article in journal (Refereed) Published
Abstract [en]

Adsorption properties of bottle-brush polyelectrolytes have been investigated using dual polarization interferometry (DPI), which provides real time monitoring of adsorbed layer thickness and refractive index. The adsorption on silicon oxynitride was carried out from aqueous solution with no added inorganic salt, and the adsorbed polyelectrolyte layer was subsequently rinsed with NaCl solutions of increasing concentration. The bottle-brush polyelectrolytes investigated in this study have different ratios of permanent cationic charged segments and uncharged PEO side chains. Both the cationic groups and the PEO side chains have affinity for silica-like surfaces, and thus contribute to the adsorption process that becomes rather complex. Adsorption properties in water, responses to changes in ionic strength of the surrounding medium, adsorption kinetics and the layer structure are all strongly dependent on the ratio between backbone charges and side chains. The results are interpreted in terms of competitive adsorption of segments with different chemical nature. The adsorption kinetics is relatively fast, taking only tens to hundreds of seconds when adsorbed from dilute 100 ppm solutions. The DPI technique was found to be suitable for studying such rapid adsorption processes, including determination of the initial adsorption kinetics. We expect that the effects observed in this study are of general importance for synthetic and biological polymers carrying segments of different nature.

Keyword
Bottle-brush polyelectrolyte, Dual polarization interferometry, Adsorption, Desorption, Adsorption mechanism, Adsorption kinetics, Silicon oxynitride
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-12951 (URN)10.1016/j.jcis.2010.03.067 (DOI)000278924600024 ()20403606 (PubMedID)2-s2.0-77953620714 (ScopusID)
Note
QC 20100520Available from: 2010-05-20 Created: 2010-05-20 Last updated: 2011-05-16Bibliographically approved
4. Adsorption and Solution Properties of Water - Soluble Moleculat Bottle - Brush Polyelectrolyte Complexes: Effect of Stoichiometry and Molecular Weight
Open this publication in new window or tab >>Adsorption and Solution Properties of Water - Soluble Moleculat Bottle - Brush Polyelectrolyte Complexes: Effect of Stoichiometry and Molecular Weight
(English)Manuscript (preprint) (Other academic)
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-33738 (URN)
Note
QS 2011Available from: 2011-05-16 Created: 2011-05-16 Last updated: 2011-05-16Bibliographically approved
5. Cationic PNIPAAM Block Copolymer Adsorption on Silicon Oxynitride: Effects of the Length of the Charged Block
Open this publication in new window or tab >>Cationic PNIPAAM Block Copolymer Adsorption on Silicon Oxynitride: Effects of the Length of the Charged Block
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-33739 (URN)
Note
QS 2011Available from: 2011-05-16 Created: 2011-05-16 Last updated: 2012-02-22Bibliographically approved

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