Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks

I.A. van Hees, P.J.M. Swinkels, R.G. Fokkink, A.H. Velders, I.K. Voets, J. van der Gucht, M. Kamperman (Corresponding author)

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

Uittreksel

The assembly of oppositely charged block copolymers, containing small thermoresponsive moieties, was investigated as a function of salt concentration and temperature. Aqueous solutions of poly-[N-isopropylacrylamide]-b-poly[dimethylaminoethyl methacrylate] (NIPAM44-b-DMAEMA216) and PNIPAM-b-poly[acrylic acid]-b-PNIPAM (NIPAM35-b-AA200-b-NIPAM35) were mixed in equal charge stoichiometry, and analysed by light scattering (LS), NMR spectroscopy and small angle X-ray scattering (SAXS). At room temperature, two different micelle morphologies were found at different salt concentrations. At NaCl concentrations below 0.75 M, complex coacervate core micelles (C3M) with a PNIPAM corona were formed as a result of interpolyelectrolyte complexation. At NaCl concentrations exceeding 0.75 M, the C3M micelles inverted into PNIPAM cored micelles (PCM), containing a water soluble polyelectrolyte corona. This behavior is ascribed to the salt concentration dependence of both the lower critical solution temperature (LCST) of PNIPAM, and the complex coacervation. Above 0.75 M NaCl, the PNIPAM blocks are insoluble in water at room temperature, while complexation between the polyelectrolytes is prevented because of charge screening by the salt. Upon increasing the temperature, both types of micelles display a cloud point temperature (Tcp), despite the small thermoresponsive blocks, and aggregate into hydrogels. These hydrogels consist of a complexed polyelectrolyte matrix with microphase separated PNIPAM domains. Controlling the morphology and aggregation of temperature sensitive polyelectrolytes can be an important tool for drug delivery systems, or the application and hardening of underwater glues.

TaalEngels
Pagina's3127-3134
Aantal pagina's8
TijdschriftPolymer Chemistry
Volume10
Nummer van het tijdschrift23
DOI's
StatusGepubliceerd - 21 jun 2019

Vingerafdruk

Polyelectrolytes
Self assembly
Block copolymers
Micelles
Temperature
Salts
Hydrogels
carbopol 940
Complexation
Glues
Methacrylates
poly-N-isopropylacrylamide
Water
X ray scattering
Stoichiometry
Light scattering
Drug Delivery Systems
Nuclear magnetic resonance spectroscopy
Acrylics
Hardening

Citeer dit

van Hees, I. A., Swinkels, P. J. M., Fokkink, R. G., Velders, A. H., Voets, I. K., van der Gucht, J., & Kamperman, M. (2019). Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks. Polymer Chemistry, 10(23), 3127-3134. DOI: 10.1039/c9py00250b
van Hees, I.A. ; Swinkels, P.J.M. ; Fokkink, R.G. ; Velders, A.H. ; Voets, I.K. ; van der Gucht, J. ; Kamperman, M./ Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks. In: Polymer Chemistry. 2019 ; Vol. 10, Nr. 23. blz. 3127-3134
@article{c7fadc598c3647b6aa1d64a1edc8ae99,
title = "Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks",
abstract = "The assembly of oppositely charged block copolymers, containing small thermoresponsive moieties, was investigated as a function of salt concentration and temperature. Aqueous solutions of poly-[N-isopropylacrylamide]-b-poly[dimethylaminoethyl methacrylate] (NIPAM44-b-DMAEMA216) and PNIPAM-b-poly[acrylic acid]-b-PNIPAM (NIPAM35-b-AA200-b-NIPAM35) were mixed in equal charge stoichiometry, and analysed by light scattering (LS), NMR spectroscopy and small angle X-ray scattering (SAXS). At room temperature, two different micelle morphologies were found at different salt concentrations. At NaCl concentrations below 0.75 M, complex coacervate core micelles (C3M) with a PNIPAM corona were formed as a result of interpolyelectrolyte complexation. At NaCl concentrations exceeding 0.75 M, the C3M micelles inverted into PNIPAM cored micelles (PCM), containing a water soluble polyelectrolyte corona. This behavior is ascribed to the salt concentration dependence of both the lower critical solution temperature (LCST) of PNIPAM, and the complex coacervation. Above 0.75 M NaCl, the PNIPAM blocks are insoluble in water at room temperature, while complexation between the polyelectrolytes is prevented because of charge screening by the salt. Upon increasing the temperature, both types of micelles display a cloud point temperature (Tcp), despite the small thermoresponsive blocks, and aggregate into hydrogels. These hydrogels consist of a complexed polyelectrolyte matrix with microphase separated PNIPAM domains. Controlling the morphology and aggregation of temperature sensitive polyelectrolytes can be an important tool for drug delivery systems, or the application and hardening of underwater glues.",
author = "{van Hees}, I.A. and P.J.M. Swinkels and R.G. Fokkink and A.H. Velders and I.K. Voets and {van der Gucht}, J. and M. Kamperman",
year = "2019",
month = "6",
day = "21",
doi = "10.1039/c9py00250b",
language = "English",
volume = "10",
pages = "3127--3134",
journal = "Polymer Chemistry",
issn = "1759-9954",
publisher = "Royal Society of Chemistry",
number = "23",

}

van Hees, IA, Swinkels, PJM, Fokkink, RG, Velders, AH, Voets, IK, van der Gucht, J & Kamperman, M 2019, 'Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks' Polymer Chemistry, vol. 10, nr. 23, blz. 3127-3134. DOI: 10.1039/c9py00250b

Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks. / van Hees, I.A.; Swinkels, P.J.M.; Fokkink, R.G.; Velders, A.H.; Voets, I.K.; van der Gucht, J.; Kamperman, M. (Corresponding author).

In: Polymer Chemistry, Vol. 10, Nr. 23, 21.06.2019, blz. 3127-3134.

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

TY - JOUR

T1 - Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks

AU - van Hees,I.A.

AU - Swinkels,P.J.M.

AU - Fokkink,R.G.

AU - Velders,A.H.

AU - Voets,I.K.

AU - van der Gucht,J.

AU - Kamperman,M.

PY - 2019/6/21

Y1 - 2019/6/21

N2 - The assembly of oppositely charged block copolymers, containing small thermoresponsive moieties, was investigated as a function of salt concentration and temperature. Aqueous solutions of poly-[N-isopropylacrylamide]-b-poly[dimethylaminoethyl methacrylate] (NIPAM44-b-DMAEMA216) and PNIPAM-b-poly[acrylic acid]-b-PNIPAM (NIPAM35-b-AA200-b-NIPAM35) were mixed in equal charge stoichiometry, and analysed by light scattering (LS), NMR spectroscopy and small angle X-ray scattering (SAXS). At room temperature, two different micelle morphologies were found at different salt concentrations. At NaCl concentrations below 0.75 M, complex coacervate core micelles (C3M) with a PNIPAM corona were formed as a result of interpolyelectrolyte complexation. At NaCl concentrations exceeding 0.75 M, the C3M micelles inverted into PNIPAM cored micelles (PCM), containing a water soluble polyelectrolyte corona. This behavior is ascribed to the salt concentration dependence of both the lower critical solution temperature (LCST) of PNIPAM, and the complex coacervation. Above 0.75 M NaCl, the PNIPAM blocks are insoluble in water at room temperature, while complexation between the polyelectrolytes is prevented because of charge screening by the salt. Upon increasing the temperature, both types of micelles display a cloud point temperature (Tcp), despite the small thermoresponsive blocks, and aggregate into hydrogels. These hydrogels consist of a complexed polyelectrolyte matrix with microphase separated PNIPAM domains. Controlling the morphology and aggregation of temperature sensitive polyelectrolytes can be an important tool for drug delivery systems, or the application and hardening of underwater glues.

AB - The assembly of oppositely charged block copolymers, containing small thermoresponsive moieties, was investigated as a function of salt concentration and temperature. Aqueous solutions of poly-[N-isopropylacrylamide]-b-poly[dimethylaminoethyl methacrylate] (NIPAM44-b-DMAEMA216) and PNIPAM-b-poly[acrylic acid]-b-PNIPAM (NIPAM35-b-AA200-b-NIPAM35) were mixed in equal charge stoichiometry, and analysed by light scattering (LS), NMR spectroscopy and small angle X-ray scattering (SAXS). At room temperature, two different micelle morphologies were found at different salt concentrations. At NaCl concentrations below 0.75 M, complex coacervate core micelles (C3M) with a PNIPAM corona were formed as a result of interpolyelectrolyte complexation. At NaCl concentrations exceeding 0.75 M, the C3M micelles inverted into PNIPAM cored micelles (PCM), containing a water soluble polyelectrolyte corona. This behavior is ascribed to the salt concentration dependence of both the lower critical solution temperature (LCST) of PNIPAM, and the complex coacervation. Above 0.75 M NaCl, the PNIPAM blocks are insoluble in water at room temperature, while complexation between the polyelectrolytes is prevented because of charge screening by the salt. Upon increasing the temperature, both types of micelles display a cloud point temperature (Tcp), despite the small thermoresponsive blocks, and aggregate into hydrogels. These hydrogels consist of a complexed polyelectrolyte matrix with microphase separated PNIPAM domains. Controlling the morphology and aggregation of temperature sensitive polyelectrolytes can be an important tool for drug delivery systems, or the application and hardening of underwater glues.

UR - http://www.scopus.com/inward/record.url?scp=85067121016&partnerID=8YFLogxK

U2 - 10.1039/c9py00250b

DO - 10.1039/c9py00250b

M3 - Article

VL - 10

SP - 3127

EP - 3134

JO - Polymer Chemistry

T2 - Polymer Chemistry

JF - Polymer Chemistry

SN - 1759-9954

IS - 23

ER -

van Hees IA, Swinkels PJM, Fokkink RG, Velders AH, Voets IK, van der Gucht J et al. Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks. Polymer Chemistry. 2019 jun 21;10(23):3127-3134. Beschikbaar vanaf, DOI: 10.1039/c9py00250b