ABSTRACT
Two series of pyrene-labeled poly(oligo(ethylene glycol) methyl ether methacrylate)s referred to as PyEG5-PEGnMA and PyC4-PEGnMA were prepared to probe the region surrounding the polymethacrylate backbone by using the fluorescence of the dye pyrene. PyEG5-PEGnMA and PyC4-PEGnMA were prepared by copolymerizing the EGnMA methacrylate monomers with penta(ethylene glycol) 1-pyrenemethyl ether methacrylate or 1-pyrenebutyl methacrylate, respectively. In organic solvents, the much longer 18 non-hydrogen atom linker connecting the pyrene moieties to the polymethacrylate backbone in the PyEG5-PEGnMA samples enabled the deployment of the pyrenyl labels into the solution. In water, however, an excited pyrene for PyEG5-PEGnMA was found to probe a same volume as for the PyC4-PEGnMA samples where a much shorter 6 non-hydrogen atom spacer connected pyrene to the backbone. Another surprising observation, considering that the hydrophobicity of pyrene induces strong pyrene aggregation for many pyrene-labeled water-soluble polymers (Py-WSPs) in water, was the little pyrene aggregation found for the PyEG5-PEGnMA and PyC4-PEGnMA samples in water. These effects could be related to the organic-like domain (OLD) generated by the oligo(ethylene glycol) side chains densely arranged around the polymethacrylate backbone of the polymeric bottlebrush (PBB). Additional fluorescence experiments conducted with the penta(ethylene glycol) 1-pyrenemethyl ether derivative indicated that the cylindrical OLD surrounding the polymethacrylate backbone had a chemical composition similar to that of ethylene glycol. Binding of hydrophobic pyrene molecules to unlabeled PEGnMA bottlebrushes in water further supported the existence of the OLD. The demonstration, that PEGnMA samples form an OLD in water, which can host and protect hydrophobic cargoes like pyrene, should lead to the development of improved PEGnMA-based drug delivery systems.
ABSTRACT
Proteins in solution tend to coat solid surfaces upon exposure. Depending on the nature of the surface, the environmental conditions, and the nature of the protein these adsorbed proteins may self-assemble into ordered, fibre-like structures called amyloids. Nanoparticulate surfaces, with their high surface to volume ratio, are particularly favourable to amyloid formation. Most prior research has focussed on either inorganic or organic nanoparticles in solution. In this research, we instead focus on aerogels created from TEMPO-oxidized cellulose nanofibers (TO-CNF) to serve as bio-based, three-dimensional amyloid templates with a tuneable surface chemistry. Previous research on the use of cellulose as a protein adsorption template has shown no evidence of a change in the secondary protein structure. Herein, however, with the aid of the reducing agent TCEP, we were able to induce the formation of amyloid-like 'worms' on the surface of TO-CNF aerogels. Furthermore, we demonstrate that the addition of the TO-CNF aerogel can also induce bulk aggregation under conditions where it previously did not exist. Finally, we show that the addition of the aerogel increases the rate of 'worm' formation in conditions where previous research has found a long lag-phase. Therefore, TO-CNF aerogels are shown to be excellent templates for inducing ordered protein aggregation.
Subject(s)
Nanofibers , Gels/chemistry , Nanofibers/chemistry , Cellulose/chemistry , Amyloidogenic Proteins , AdsorptionABSTRACT
Seven pyrene-labeled poly(oligo(ethylene glycol) methyl ether methacrylate)s (PyEG5-PEGnMAs) were prepared with n = 0, 3, 4, 5, 7, 9, and 19 ethylene glycol units by copolymerizing a small amount of penta(ethylene glycol) 1-pyrenemethyl ether methacrylate with an EGnMA monomer. The conformation of the PyEG5-PEGnMA polymers evolved from a random coil for PyEG5-PEG0MA or poly(methyl methacrylate) to a polymeric bottle brush (PBB) architecture with increasing side chain length. The fluorescence decays of the PyEG5-PEGnMA samples were fitted according to the fluorescence blob model (FBM) whose parameters were used, in combination with the Kratky-Porod equation, to calculate the persistence length of these polymers. The persistence lengths obtained from the PEF experiments were found to increase with the square of the number (NS) of non-hydrogen atoms in the side chain as expected theoretically. The persistence lengths found with the PyEG5-PEGnMA samples in DMF also matched those found earlier for another series of PEGnMA samples labeled with 1-pyrenebutanol. The good agreement found between the persistence lengths obtained with the PEGnMA samples labeled with two different pyrene derivatives illustrates the robustness of the method and its applicability for measuring the unknown persistence length of polydisperse polymer samples.
ABSTRACT
The model-free analysis (MFA) was applied to measure the average rate constant (
ABSTRACT
A poly(dimethylsiloxane-co-(3-aminopropyl)methylsiloxane) polymer (PDMS with 20.3 mol % of (3-aminopropyl)methyl siloxane monomer) has been labeled randomly with 1-pyreneacetyl groups to generate a series of polysiloxanes (Py-PDMS) with pyrenyl contents ranging from 0.7 mol % to 5.2 mol % of the total number of structural units. The remainder of the amino groups were acetylated to avoid intra-chain quenching of the excited singlet states of pyrene via exciplex formation with free amino groups while allowing the formation of excimers to proceed. The fluorescence spectra and temporal decays of the Py-PDMS samples were acquired in tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and dioxane.