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Thermoresponsive polymer coated gold nanoparticles: from MADIX/RAFT copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to salt and temperature induced nanoparticle aggregation

Samarendra Maji (UGent) , Zhiyue Zhang (UGent) , Lenny Voorhaar (UGent) , Sophie Pieters, Birgit Stubbe (UGent) , Sandra Van Vlierberghe (UGent) , Peter Dubruel (UGent) , Bruno De Geest (UGent) and Richard Hoogenboom (UGent)
(2015) RSC ADVANCES. 5(53). p.42388-42398
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Abstract
In the present contribution, we report the MADIX/RAFT polymerization for the synthesis of thermoresponsive homo and statistical copolymers of N-vinylcaprolactam (NVCL) and N-vinylpyrrolidone (NVP). The conditions for the polymerization of NVP were optimized using an automated parallel synthesizer and these optimal conditions were applied for preparing copolymers with systematical variation in composition. The cloud point temperatures (T-CP's) of aqueous solutions of PNVCL and P(NVCL-stat-NVP)'s (CP1-CP5) were found to be tuneable between 40 degrees C and >95 degrees C at 5 mg mL(-1). Next, stable colloidal solutions of AuNPs coated with PNVCL and CP1-CP5 were obtained via an exchange reaction of pre-synthesized citrate stabilized AuNPs with PNVCL and CP1-CP5 by a direct 'grafting to' approach. The maximum absorbance wavelength (lambda(max)) of the surface plasmon resonance (SPR) band and size of all the thermoresponsive polymer coated AuNPs were found to be almost unchanged up to 65 degrees C (above the T-CP of PNVCL and CP5) in MilliQ water which is presumably due to electrostatic stabilization of the AuNPs by residual citrate groups on the surface. However, in 0.1 M NaCl aqueous solution the lambda(max) of the thermoresponsive AuNPs were red shifted when heated up to 65 degrees C which is attributed to the screening of the citrate negative charges on the surface of AuNPs that suppress electrostatic stabilization enabling T-induced aggregation leading to a shift in the SPR band. These thermoresponsive AuNPs may find applications as colorimetric temperature and/or salt sensors.
Keywords
REVERSIBLE-ADDITION, DRUG-DELIVERY SYSTEMS, RAFT POLYMERIZATION, DIBLOCK COPOLYMERS, AQUEOUS-SOLUTIONS, BLOCK-COPOLYMERS, POLY(N-VINYLCAPROLACTAM), BEHAVIOR, CHAIN-TRANSFER POLYMERIZATION, CONTROLLED RADICAL POLYMERIZATION

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MLA
Maji, Samarendra et al. “Thermoresponsive Polymer Coated Gold Nanoparticles: From MADIX/RAFT Copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to Salt and Temperature Induced Nanoparticle Aggregation.” RSC ADVANCES 5.53 (2015): 42388–42398. Print.
APA
Maji, S., Zhang, Z., Voorhaar, L., Pieters, S., Stubbe, B., Van Vlierberghe, S., Dubruel, P., et al. (2015). Thermoresponsive polymer coated gold nanoparticles: from MADIX/RAFT copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to salt and temperature induced nanoparticle aggregation. RSC ADVANCES, 5(53), 42388–42398.
Chicago author-date
Maji, Samarendra, Zhiyue Zhang, Lenny Voorhaar, Sophie Pieters, Birgit Stubbe, Sandra Van Vlierberghe, Peter Dubruel, Bruno De Geest, and Richard Hoogenboom. 2015. “Thermoresponsive Polymer Coated Gold Nanoparticles: From MADIX/RAFT Copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to Salt and Temperature Induced Nanoparticle Aggregation.” Rsc Advances 5 (53): 42388–42398.
Chicago author-date (all authors)
Maji, Samarendra, Zhiyue Zhang, Lenny Voorhaar, Sophie Pieters, Birgit Stubbe, Sandra Van Vlierberghe, Peter Dubruel, Bruno De Geest, and Richard Hoogenboom. 2015. “Thermoresponsive Polymer Coated Gold Nanoparticles: From MADIX/RAFT Copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to Salt and Temperature Induced Nanoparticle Aggregation.” Rsc Advances 5 (53): 42388–42398.
Vancouver
1.
Maji S, Zhang Z, Voorhaar L, Pieters S, Stubbe B, Van Vlierberghe S, et al. Thermoresponsive polymer coated gold nanoparticles: from MADIX/RAFT copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to salt and temperature induced nanoparticle aggregation. RSC ADVANCES. 2015;5(53):42388–98.
IEEE
[1]
S. Maji et al., “Thermoresponsive polymer coated gold nanoparticles: from MADIX/RAFT copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to salt and temperature induced nanoparticle aggregation,” RSC ADVANCES, vol. 5, no. 53, pp. 42388–42398, 2015.
@article{6931610,
  abstract     = {In the present contribution, we report the MADIX/RAFT polymerization for the synthesis of thermoresponsive homo and statistical copolymers of N-vinylcaprolactam (NVCL) and N-vinylpyrrolidone (NVP). The conditions for the polymerization of NVP were optimized using an automated parallel synthesizer and these optimal conditions were applied for preparing copolymers with systematical variation in composition. The cloud point temperatures (T-CP's) of aqueous solutions of PNVCL and P(NVCL-stat-NVP)'s (CP1-CP5) were found to be tuneable between 40 degrees C and >95 degrees C at 5 mg mL(-1). Next, stable colloidal solutions of AuNPs coated with PNVCL and CP1-CP5 were obtained via an exchange reaction of pre-synthesized citrate stabilized AuNPs with PNVCL and CP1-CP5 by a direct 'grafting to' approach. The maximum absorbance wavelength (lambda(max)) of the surface plasmon resonance (SPR) band and size of all the thermoresponsive polymer coated AuNPs were found to be almost unchanged up to 65 degrees C (above the T-CP of PNVCL and CP5) in MilliQ water which is presumably due to electrostatic stabilization of the AuNPs by residual citrate groups on the surface. However, in 0.1 M NaCl aqueous solution the lambda(max) of the thermoresponsive AuNPs were red shifted when heated up to 65 degrees C which is attributed to the screening of the citrate negative charges on the surface of AuNPs that suppress electrostatic stabilization enabling T-induced aggregation leading to a shift in the SPR band. These thermoresponsive AuNPs may find applications as colorimetric temperature and/or salt sensors.},
  author       = {Maji, Samarendra and Zhang, Zhiyue and Voorhaar, Lenny and Pieters, Sophie and Stubbe, Birgit and Van Vlierberghe, Sandra and Dubruel, Peter and De Geest, Bruno and Hoogenboom, Richard},
  issn         = {2046-2069},
  journal      = {RSC ADVANCES},
  keywords     = {REVERSIBLE-ADDITION,DRUG-DELIVERY SYSTEMS,RAFT POLYMERIZATION,DIBLOCK COPOLYMERS,AQUEOUS-SOLUTIONS,BLOCK-COPOLYMERS,POLY(N-VINYLCAPROLACTAM),BEHAVIOR,CHAIN-TRANSFER POLYMERIZATION,CONTROLLED RADICAL POLYMERIZATION},
  language     = {eng},
  number       = {53},
  pages        = {42388--42398},
  title        = {Thermoresponsive polymer coated gold nanoparticles: from MADIX/RAFT copolymerization of N-vinylpyrrolidone and N-vinylcaprolactam to salt and temperature induced nanoparticle aggregation},
  url          = {http://dx.doi.org/10.1039/c5ra06559c},
  volume       = {5},
  year         = {2015},
}

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