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At least 1,063 records · Page 59

Cyanine-Incorporated Amorphous Polymeric Carbon Dots for Optical Reactive Oxygen Species Sensing

Reactive oxygen species (ROS) are common cellular oxidants that when overproduced by cellular stressors cause harm to cells. Detection of ROS is of utmost importance to understanding a wide variety of cellular function and toxicity mechanisms. Conventional ROS fluorescence assays involve using a single dye to visualize the ROS quantity. Herein, we describe ROS-sensitive, fluorescent-dye-incorporated carbon dots with dual fluorescence capabilities and good biocompatibility. Carbon dots (CDs) made of citric acid and urea were synthesized with incorporated cyanine-3-amine (Cy3), a bright red fluorescent dye, to create Cy3-CDs. Additionally, to get Cy3 into the ROS-sensitive form, this work demonstrated that Cy3 alone and Cy3 within carbon dots can be electrochemically reduced to their colorless ROS-sensitive form. Cy3, CDs, and Cy3-CDs are all responsive to additions of superoxide, leading to an increase in the fluorescence. Overall, this work examines how O 2 •– and additional oxidizers interact with CDs, Cy3, and Cy3-CDs, and molecular-level hypotheses are explored that will inform the design of future carbon dot-based ROS sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics of Polymerization and Gelation in Epoxy Nanocomposites via X-ray Photon Correlation Spectroscopy

The details of the curing process of epoxy resins are notoriously difficult to ascertain, hampering polymer matrix composite manufacturing. Here, the curing of a series of six epoxy resins containing dilute spherical nanoparticles was investigated via X-ray photon correlation spectroscopy (XPCS). The resin formulation was varied to achieve a range of crosslink densities and topologies. Prior to gelation, the viscosities obtained from XPCS agreed with bulk rheology. A clear dynamic transition was detected in all samples, where the q-scaling changes from approximately q2 .2 to q 1 , indicating a transition from sub-diffusive to ballistic-like nanoparticle motion. For the samples with a high crosslink density, this change was abrupt and coincided with gelation, and there was no evidence of crosslink heterogeneity. Chain entanglement played a role in the transition for samples with lower crosslink density. Finally, this work reveals the potential of XPCS to deliver new quantitative insights into the curing process of thermosetting resins.

36 MATERIALS SCIENCE↗

Crosslinking and Gelation of Polymer Brushes and Free Polymer Chains in a Confined Space during Controlled Radical Polymerization-A Computer Simulation Study

The confinement effect on crosslinking and gelation during controlled/living copolymerization of a monovinyl and a divinyl monomer was studied by Monte Carlo computer simulation using the dynamic lattice liquid method. The simulated reactions took place in plane-parallel slits of various widths for various grafting densities (GDs) and various initial initiator/crosslinker ratios ([X] 0 /[Ini] 0 ). Monomers and crosslinkers were initially randomly distributed in the slit, but initiators were either anchored to one solid plane (polymer brushes) or randomly distributed (free chains). For brushes, the gel point (GP) depended on GD and [X] 0 /[Ini] 0 . The higher these parameters, the lower was the gel point. The gel point was also affected by the slit width. For free, nongrafted chains, the dependence of GP on slit width was negligible. For brushes, a nonuniform density of crosslinks was found, the highest density was close to the wall. This asymmetry was high at the gel point and decreased at higher conversions.

36 MATERIALS SCIENCE↗