Stimuli-Responsive Polyelectrolyte Brushes As a Matrix for the Attachment of Gold Nanoparticles: The Effect of Brush Thickness on Particle Distribution

Christau, Stephanie; Thurandt, Stefan; Yenice, Zuleyha; Klitzing, Regine von

doi:10.3390/polym6071877

Cited by 43 publications

(57 citation statements)

References 65 publications

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“…In order to apply this equation, one requires estimates of the dry thickness: the water content of the ambient dry brushes (rh = 30%) is ≈2.5% is extracted from ref 30 and was used to calculate the dry thicknesses.…”

Section: Atomic Force Microscopy (Afm) Measurementsmentioning

confidence: 99%

“…These results are in very good agreement with the work of Christau et al, who investigated the effect of polymer brush thickness on the distribution of the deposited nanoparticles. 30 They concluded that the particle number density increases with brush thickness, which can be attributed to the increased roughness of the thicker brush. The particle number density was calculated using ImageJ.…”

Section: Articlementioning

confidence: 99%

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Thermoresponsive PDMAEMA Brushes: Effect of Gold Nanoparticle Deposition

Yenice¹,

Schön²,

Bildirir³

et al. 2015

J. Phys. Chem. B

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The paper addresses the effect of gold nanoparticle (Au-NP) deposition on the thermoresponsive volume phase transition of the weak polyelectrolyte poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes. PDMAEMA brushes were synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP). The PDMAEMA/Au-NP composite brushes were fabricated by immersing the brush modified wafer in the Au-NP suspension. Atomic force microscopy (AFM), ellipsometry, and scanning electron microscopy (SEM) have been employed to characterize the neat PDMAEMA brushes and PDMAEMA/Au-NP composite brushes. All neat PDMAEMA brushes swelled below the volume phase transition temperature and collapsed with increasing temperature over a broad temperature range independent of the initial brush thickness. Water uptake of the brushes is also independent of initial brush thickness. The adsorption of the charged Au-NPs significantly affects the degree of swelling and the thermoresponsive properties of the brushes. PDMAEMA/Au-NP composite brushes do not exhibit any noticeable phase transition at the experimental temperature range irrespective of the initial brush thickness. The reason for this behavior is attributed to a combination of the following: the decreased conformational entropy of the Au-NP adsorbed polymer chains, the increased hydrophilicity of the system due to the charged Au-NPs, and the ≈13 nm diameter Au-NPs causing steric hindrance. We have also shown that the AFM full-indentation method can be successfully applied to determine the polymer brush thicknesses.

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Section: Atomic Force Microscopy (Afm) Measurementsmentioning

confidence: 99%

Section: Articlementioning

confidence: 99%

Thermoresponsive PDMAEMA Brushes: Effect of Gold Nanoparticle Deposition

Yenice¹,

Schön²,

Bildirir³

et al. 2015

J. Phys. Chem. B

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“…Molecules commonly used at this step are organothiols in the case of gold [18][19] or organosilanes for oxidized silicon and glass surfaces [20][21] . More recently, polymer-based coating was applied to attach AuNP on planar substrates [22][23] . Poly(ethylene glycol) (PEG) is particularly adapted to biosensing applications by forming smooth and uniform PEG films that inhibit non specific adsorption [24][25] and provide a high affinity to citrate-stabilized gold nanoparticles [26][27] .…”

Section: Introductionmentioning

confidence: 99%

Gold Nanoparticles Assembly on Silicon and Gold Surfaces: Mechanism, Stability, and Efficiency in Diclofenac Biosensing

et al. 2016

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We investigated the assembly of Gold nanoparticles (AuNPs) on Gold and Silicon sensors with two final objectives: (i) understanding the factors governing the interaction and (ii) building up a nanostructured piezoelectric immunosensor for diclofenac, a small-sized pharmaceutical pollutant. Different surface chemistries were devised to achieve AuNPs assembly on planar substrates. These surface chemistries included amines to immobilize AuNPs via electrostatic interaction, or a mixture of amines and thiols to covalently attach the AuNPs. We also generated PEG-amine terminated surfaces to benefit from the well-known non-biofouling properties of PEG-coated surfaces. The functional substrates and the resulting gold nanoparticle layers were characterized in detail by Surface IR, contact angle measurements and Scanning Electron Microscopy (SEM). The mechanism of adsorption is discussed herein considering the nature of the terminal groups and their charge at the pH of AuNPs adsorption. The coverage and the dispersion of AuNPs were strongly dependent on the anchoring points on the surfaces; the optimal were reached when the attachment layer offered multiple interaction points, in particular, for NH 2 /SH and PEG/NH 2 terminated surfaces, where the percentage of isolated particles was up to 78 %. In addition, PEG-coated surfaces led to a stable AuNPs layer resistant to ultrasounds and to further functionalization of the immobilized nanoparticles. These surfaces were used to engineer quartz crystal microbalance (QCM) biosensors for diclofenac detection. The AuNPs nanostructured substrates significantly enhanced the biosensor sensitivity as compared to planar substrates (up to 6 times higher). This enhancement presages a higher sensitivity in the competitive detection of diclofenac on these systems. More importantly, despite the biorecognition and the drastic regeneration conditions, SEM images show that gold nanoparticles layers are stable and reliable, which paves the way for their use as nanostructured platforms for multiple applications.

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“…This makes them particularly interesting for controlled release, 7 tunable assembly of coated nanoparticles, 8 responsive nanoactuators 9,10 or for antifouling surfaces. 11,12 More recently, complex systems produced by embedding surfactants, 13,14 gels 15,16 or nanoparticles [17][18][19][20] into polymer brushes have been studied, from which multiresponsive coatings with enlarged applicability as stimuli-responsive systems can be designed. Among them, there are some examples of polyelectrolyte (PE) chains adsorbed onto charged polymer brushes.…”

Section: Introductionmentioning

confidence: 99%

Temperature responsive behavior of polymer brush/polyelectrolyte multilayer composites

et al. 2016

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aThe complex interaction of polyelectrolyte multilayers (PEMs) physisorbed onto end-grafted polymer brushes with focus on the temperature-responsive behavior of the system is addressed in this work. The investigated brush/multilayer composite consists of a poly(styrene sulfonate)/poly(diallyldimethylammonium chloride) (PSS/PDADMAC) multilayer deposited onto the poly(N-isopropylacrylamide-bdimethylaminoethyl methacrylate) P(NIPAM-b-DMAEMA) brush. Ellipsometry and neutron reflectometry were used to monitor the brush collapse with the thickness decrease as a function of temperature and the change in the monomer distribution perpendicular to the substrate at temperatures below, across and above the phase transition, respectively. It was found that the adsorption of PEMs onto polymer brushes had a hydrophobization effect on PDMAEMA, inducing the shift of its phase transition to lower temperatures, but without suppressing its temperature-responsiveness. Moreover, the diffusion of the free polyelectrolyte chains inside the charged brush was proved by comparing the neutron scattering length density profile of pure and the corresponding PEM-capped brushes, eased by the enhanced contrast between hydrogenated brushes and deuterated PSS chains. The results presented herein demonstrate the possibility of combining a temperature-responsive brush with polyelectrolyte multilayers without quenching the responsive behavior, even though significant interpolyelectrolyte interactions are present. This is of importance for the design of multicompartment coatings, where the brush can be used as a reservoir for the controlled release of substances and the multilayer on the top as a membrane to control the diffusion in/out by applying different stimuli.

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Stimuli-Responsive Polyelectrolyte Brushes As a Matrix for the Attachment of Gold Nanoparticles: The Effect of Brush Thickness on Particle Distribution

Cited by 43 publications

References 65 publications

Thermoresponsive PDMAEMA Brushes: Effect of Gold Nanoparticle Deposition

Thermoresponsive PDMAEMA Brushes: Effect of Gold Nanoparticle Deposition

Gold Nanoparticles Assembly on Silicon and Gold Surfaces: Mechanism, Stability, and Efficiency in Diclofenac Biosensing

Temperature responsive behavior of polymer brush/polyelectrolyte multilayer composites

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