Self-Reporting Degradable Fluorescent Grafted Copolymer Micelles Derived from Biorenewable Resources

Abstract

A series of hydrolytically degradable fluorescent poly(ferulic acid-co-tyrosine)-g-mPEG graft copolymers were synthesized and shown to undergo self-assembly in aqueous media to yield fluorescent micelles. The polymers and their micellar assemblies exhibited greater fluorescence emission intensity than did their small molecular building blocks, which provides a self-reporting character that has potential for monitoring the polymer integrity and also for performing in theranostics applications. The amphiphilic graft-copolymers were synthesized by Cu-assisted azide–alkyne “click” addition of azido-functionalized mPEG polymers onto fluorescent degradable hydrophobic copolymers displaying randomly distributed alkyne side-chain groups along their biorenewably derived poly(ferulic acid-co-tyrosine) backbones. The morphologies and photophysical properties of the supramolecular assemblies generated in aqueous solutions were evaluated by DLS, TEM, AFM, and steady-state optical spectroscopies. The 15–30 nm sized micelles behaved as broad-band emitters in the 350–600 nm range, which highlights their potential as self-reporting nanomaterials for in vitro studies.

Hierarchical excluded volume screening in solutions of bottlebrush polymers

“…The variation of architecture, i.e., length and grafting density of side chains, allows for systematic tuning of molecular conformation and physical properties of bottlebrushes [14]. These unique features make bottlebrushes candidates for diverse applications including super-soft elastomers [15,16], drug delivery agents [17], molecular sensors [18], stimuli-responsive [19][20][21] and protective surfaces [22], emulsifiers [23], lubricants [24], porous [25], self-assembled [26,27], and thermoplastic [28] materials, photolithography [29], ionic transport [30], photonics [31], and energy storage [32]. In addition, bottlebrush macromolecules are of great importance in biology, since a myriad of bottlebrush-like glycoproteins and proteoglycans regulate crucial functions in the human body including clearance of lungs [33], joint lubrication [34], and cell protection [35].…”

Fluorescent Block Copolymer Micelles That Can Self-Report on Their Assembly and Small Molecule Encapsulation

“… 23 For example, the aggregation of dye labeled polymers can cause quenching processes to be enhanced or inhibited, leading upon micellization to decreased or increased emission, respectively. 24 , 25 The degradation of polymer micelles derived from intrinsically fluorescent copolymers has also been observed by detecting a decrease in emission, 26 while the loss of mobility upon BCP micelle gelation has allowed for the glass transition temperature and critical micelle temperature to be measured by changes in emission from a covalently attached fluorophore. 27 Changes in the morphology of BCP assemblies can also be observed by measuring emission from fluorescent labels.…”

Synthesis and application of a novel environmental plasticizer based on cardanol for poly(vinyl chloride)

“…the application range of phthalates is a tendency in the future [6][7][8][9] . Moreover, petroleum shortages and environmental concerns have encouraged extensive researches on chemical products based on renewable resources [10][11][12][13][14] . As a result, there is a growing interest in the use of bio-based plasticizers that are characterized by sustainability, availability and low cost.…”