ABSTRACT
We report on the synthesis and characterization of poly(diethylene glycol methylether methacrylate) (PDEGMA) brushes by surface-initiated atom transfer radical polymerization inside ordered cylindrical nanopores of anodic aluminum oxide with different pore radii between 20 and 185 nm. In particular, the dependence of polymerization kinetics and the degree of pore filling on the interfacial curvature were analyzed. On the basis of field emission scanning electron microscopy data and thermal gravimetric analysis (TGA), it was concluded that the polymerization rate was faster at the pore orifice compared to the pore interior and also as compared to the analogous reaction carried out on flat aluminum oxide substrates. The apparent steady-state polymerization rate near the orifice increased with decreasing pore size. Likewise, the overall apparent polymerization rate estimated from TGA data indicated stronger confinement for pores with increased curvature as well as increased mass transport limitations due to the blockage of the pore orifice. Only for pores with a diameter to length ratio of â¼1, PDEGMA brushes were concluded to grow uniformly with constant thickness. However, because of mass transport limitations in longer pores, incomplete pore filling was observed, which leads presumably to a PDEGMA gradient brush. This study contributes to a better understanding of polymer brush-functionalized nanopores and the impact of confinement, in which the control of polymer brush thickness together with grafting density along the nanopores is key for applications of PDEGMA brushes confined inside nanopores.
ABSTRACT
The modification of cylindrical anodic aluminum oxide (AAO) nanopores by alternating layer-by-layer (LBL) deposition of poly(sodium-4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) was studied in situ by reflectometric interference spectroscopy (RIfS). In particular, the kinetics of polyelectrolyte deposition inside the pores with a diameter of 37 ± 3 nm and a length of 3.7 ± 0.3 µm were unraveled, and potential differences in the LBL multilayer growth compared to flat silicon substrates as well as the effect of different ionic strengths and different types of ions were investigated. RIfS measures the effective optical thicknesses, which is-for a constant pore length-proportional to the effective refractive index of the AAO sample, from which, in turn, the deposited mass of the polymer or the corresponding layer thickness can be estimated. Compared to the multilayer growth by the LBL deposition on the flat aminosilane-primed silicon wafers, which was assessed by spectroscopic ellipsometry, the thickness increment per deposited bilayer, as well as the dependence of this increment on the ionic strength (0.01-0.15) and the counterion type (Na+ vs Ca2+) inside the aminosilane-primed nanopores, was for the first bilayers to within the experimental error identical. For thicker multilayers, the pore diameter became smaller, which led to reduced thickness increments and eventually virtually completely filled the pores. The observed kinetics is consistent with the mass-transport-limited adsorption of the polyelectrolyte to the charged surface according to a Langmuir isotherm with a negligible desorption rate. In addition to fundamental insights into the buildup of polyelectrolyte multilayers inside the AAO nanopores, our results highlight the sensitivity of RIfS and its use as an analytical tool for probing processes inside the nanopores and for the development of biosensors.
ABSTRACT
Quadruplex DNA, which is a relevant target for anticancer therapies, may alter its conformation because of interactions with interfaces. In pursuit of a versatile methodology to probe adsorption-induced conformational changes, the interaction between a fluorescent [2.2.2]heptamethinecyanine dye and quadruplex DNA (G4-DNA) was studied in solution and on surfaces. In solution, the cyanine dye exhibits a strong light-up effect upon the association with G4-DNA without interference from double-stranded DNA. In addition, a terminal π-stacking as a binding mode between the cyanine dye and G4-DNA is concluded using NMR spectroscopy. To unravel the effects of adsorption on the conformation of quadruplex-DNA, G4-DNA, and double-stranded and single-stranded DNA were adsorbed to positively charged poly(allylamine) hydrochloride (PAH) surfaces, both in planar and in constrained 55 nm diameter aluminum oxide nanopore formats. All DNA forms showed a very strong affinity to the PAH surfaces as shown by surface plasmon resonance and reflectometric interference spectroscopy. The significant increase of the fluorescence emission intensity of the cyanine light-up probe observed exclusively for surface immobilized G4-DNA affords evidence for the adsorption of G4-DNA on PAH with retained quadruplex conformation.
