Polymer brush coatings are frequently
prepared by radical polymerization,
a notoriously oxygen sensitive process. Glucose oxidase (GOx) can
inexpensively enable radical polymerization in solution by enzymatically
consuming oxygen as it oxidizes glucose. Here, we report the growth
of polymeric brushes using GOx-assisted atom transfer radical polymerization
(ATRP) from a surface while open to air. Specifically, we grew a set
of biomedically relevant polymer brushes, including poly(oligo(ethylene
glycol) methacrylate) (POEGMA), poly(2-dimethylaminoethyl methacrylate)
(PDMAEMA), poly(sulfobetaine methacrylate) (PSBMA), and poly(2-(methylsulfinyl)ethyl
acrylate (PMSEA). For each of these polymers, we monitored GOx-assisted
and GOx-free ATRP reaction kinetics in real time using quartz crystal
microbalance (QCM) and verified findings with localized surface plasmon
resonance (LSPR). We modeled brush growth kinetics considering bimolecular
termination. This model fit our data well (r
2 > 0.987 for all samples) and shows the addition of GOx
increased
effective kinetic chain lengths, propagation rates, and reproducibility.
We tested the antifouling properties of the polymer brush coatings
against human blood plasma and were surprised to find that coatings
prepared with GOx repelled more plasma proteins in all cases than
their GOx-free counterparts.
Observations of the nighttime thermospheric wind from two ground‐based Fabry‐Perot Interferometers are compared to the level 2.1 and 2.2 data products from the Michelson Interferometer Global High‐resolution Thermospheric Imaging (MIGHTI) onboard National Aeronautics and Space Administration's Ionospheric Connection Explorer to assess and validate the methodology used to generate measurements of neutral thermospheric winds observed by MIGHTI. We find generally good agreement between observations approximately coincident in space and time with mean differences less than 11 m/s in magnitude and standard deviations of about 20–35 m/s. These results indicate that the independent calculations of the zero‐wind reference used by the different instruments do not contain strong systematic or physical biases, even though the observations were acquired during solar minimum conditions when the measured airglow intensity is weak. We argue that the slight differences in the estimated wind quantities between the two instrument types can be attributed to gradients in the airglow and thermospheric wind fields and the differing viewing geometries used by the instruments.
We present terminal deoxynucleotidyl transferase-catalyzed enzymatic polymerization (TcEP) for the template-free synthesis of high-molecular-weight, single-stranded DNA (ssDNA) and demonstrate that it proceeds by a living chain-growth polycondensation mechanism. We show that the molecular weight of the reaction products is nearly monodisperse, and can be manipulated by the feed ratio of nucleotide (monomer) to oligonucleotide (initiator), as typically observed for living polymerization reactions. Understanding the synthesis mechanism and the reaction kinetics enables the rational, template-free synthesis of ssDNA that can be used for a range of biomedical and nanotechnology applications.
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