This article reports on the synthesis of thermo- and light-sensitive hydrophilic block copolymers, poly(ethylene oxide)-b-poly(ethoxytri(ethylene glycol) acrylate-co-o-nitrobenzyl acrylate), and the study of their micellization/dissociation transitions in water in response to temperature changes and UV irradiation. The block copolymers with controlled molecular weights and narrow polydispersities were synthesized by atom transfer radical polymerization of a mixture of ethoxytri(ethylene glycol) acrylate and o-nitrobenzyl acrylate with a molar ratio of 100:10 from a PEO macroinitiator. Dynamic light scattering and fluorescence spectroscopy studies showed that these copolymers were molecularly dissolved in water at lower temperatures and self-assembled into micelles with the thermosensitive block associating into the core and the PEO block forming the corona when the temperature was above the lower critical solution temperature (LCST) of the thermosensitive block. Upon UV irradiation, the o-nitrobenzyl group was cleaved and the LCST of the thermosensitive block was increased, causing the dissociation of micelles into unimers and the release of encapsulated fluorescent dye Nile Red into water. Further increasing the temperature induced the formation of micelles again and the re-encapsulation of Nile Red. The thermo-induced formation and dissociation of micelles were reversible.

This article presents a systematic study of the effect of pH on the rheological properties of aqueous micellar gels formed from 10.0 wt % aqueous solutions of a thermo- and pH-sensitive ABA triblock copolymer, poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid)-b-poly(ethylene oxide)-b-poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid) (P(DEGEA-co-AA)-b-PEO-b-P(DEGEA-co-AA)). The block copolymer was synthesized by atom transfer radical polymerization of DEGEA and tert-butyl acrylate with a molar ratio of 100:5 from a difunctional PEO macroinitiator and subsequent removal of tert-butyl groups using trifluoroacetic acid. PDEGEA is a thermosensitive water-soluble polymer with a cloud point of 9 °C in water. The thermo-induced sol-gel transition temperature (T(sol-gel)) of the 10.0 wt % aqueous solution of P(DEGEA-co-AA)-b-PEO-b-P(DEGEA-co-AA) can be continuously and reversibly tuned over a wide temperature range by varying the solution pH. The sol-gel transition became broader with the increase of pH, which stemmed from the weaker and broader LCST transition of P(DEGEA-co-AA) blocks at higher pH values. The maximum value of dynamic storage modulus, obtained from heating ramp, and the plateau storage moduli (G(N)), evaluated from frequency sweeps at three normalized temperatures (T/T(sol-gel) = 1.025, 1.032, and 1.039), decreased with the increase of pH from 3.00 to 5.40 with the sharpest drop observed at pH = ∼4.7. The decrease in G(N) reflects the reduction of the number of bridging polymer chains and simultaneously the increase of the numbers of loops and dangling polymer chains. The ionization of carboxylic acid groups at higher pH values introduced charges onto the thermosensitive blocks and made the polymer chains more hydrophilic, facilitating the formation of loops and dangling chains in the gels. The increase in the number of dangling polymer chains with the increase of pH was supported by fluorescence spectroscopy studies, which showed that the critical micelle concentration of P(DEGEA-co-AA)-b-PEO-b-P(DEGEA-co-AA) at a temperature corresponding to T(sol-gel) was higher at a higher pH. The results reported in this article showed that both T(sol-gel) and gel strength can be tuned by varying the solution pH, providing greater design flexibility for potential applications.

Cellulose nanocrystals (CNCs) have great potential as sustainable reinforcing materials for polymers, but there are a number of obstacles to commercialization that must first be overcome. High levels of water absorption, low thermal stabilities, poor miscibility with nonpolar polymers, and irreversible aggregation of the dried CNCs are among the greatest challenges to producing cellulose nanocrystal-polymer nanocomposites. A simple, scalable technique to modify sulfated cellulose nanocrystals (Na-CNCs) has been developed to address all of these issues. By using an ion exchange process to replace Na with imidazolium or phosphonium cations, the surface energy is altered, the thermal stability is increased, and the miscibility of dried CNCs with a nonpolar polymer (epoxy and polystyrene) is enhanced. Characterization of the resulting ion exchanged CNCs (IE-CNCs) using potentiometry, inverse gas chromatography, dynamic vapor sorption, and laser scanning confocal microscopy reveals that the IE-CNCs have lower surface energies, adsorb less water, and have thermal stabilities of up to 100 °C higher than those of prepared protonated cellulose nanocrystals (H-CNCs) and 40 °C higher than that of neutralized Na-CNC. Methyl(triphenyl)phosphonium exchanged cellulose nanocrystals (MePhP-CNC) adsorbed 30% less water than Na-CNC, retained less water during desorption, and were used to prepare well-dispersed epoxy composites without the aid of a solvent and well-dispersed polystyrene nanocomposites using a melt blending technique at 195 °C. Predictions of dispersion quality and glass transition temperatures from molecular modeling experiments match experimental observations. These fiber-reinforced polymers can be used as lightweight composites in transportation, infrastructure, and renewable energy applications.

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Owing to the intriguing transitions between free-flowing liquids and free-standing gels and the associated changes in rheological properties, stimuli-induced reversible formation of aqueous micellar gels of block copolymers has received considerable interest. 1À3 Compared with chemically cross-linked hydrogels, these responsive micellar gels, especially those triggered by temperature changes, can be more advantageous for certain applications because of the in situ solÀgel transition. 1À3 For example, Jeong et al. reported injectable drug delivery systems based on aqueous solutions of block copolymers of poly(ethylene glycol) (PEO) and polylactide that can undergo cooling-induced solÀgel transitions. 3 The polymer solutions were loaded with a model drug in the sol state at an elevated temperature. Upon subcutaneous injection and cooling to the body temperature, the polymer solutions formed gels instantaneously that subsequently acted as matrices for sustained release of drug molecules.Generally, there are two types of stimuli-responsive aqueous block copolymer micellar gels: 3-dimensional network gels, in which one block, e.g., the central block of an ABA triblock copolymer, forms bridges among micellar cores of other blocks, 1a,4 and physically jammed micellar gels, in which discrete spherical micelles of block copolymers are packed into an ordered structure. 1À3,5,6 Representative examples of the latter include aqueous gels of PEOb-poly(propylene oxide)-b-PEO (PEO-b-PPO-b-PEO) triblock ABSTRACT: This article reports on the synthesis of a hydrophilic diblock copolymer composed of two distinct thermosensitive polymers with one block containing a small amount of carboxylic acid groups, poly(methoxytri(ethylene glycol) acrylate-co-acrylic acid)-b-poly(ethoxydi(ethylene glycol) acrylate) (P(TEGMA-co-AA)-b-PDEGEA), and the study of thermo-induced solÀgelÀ sol transitions of its moderately concentrated aqueous solutions at various pH values. The diblock copolymer was obtained by the removal of tert-butyl groups of P(TEGMA-co-tert-butyl acrylate)-b-PDEGEA, which was synthesized by reversible additionÀfragmentation chain transfer polymerization. PTEGMA and PDEGEA are thermosensitive polymers with lower critical solution temperatures (LCSTs) of 58 and 9°C, respectively, in water. The incorporation of a small amount of carboxylic acid groups into PTEGMA allowed the LCST of the P(TEGMA-co-AA) block to be tuned by changing the solution pH. We found that a 20 wt % aqueous solution of P(TEGMA-co-AA)-b-PDEGEA with pH of 3.11 (measured at 0°C) underwent multiple phase transitions upon heating, from a clear, free-flowing liquid (<19°C) to a clear, free-standing gel (19 to 39°C), to a clear, free-flowing hot liquid (40 to 55°C), and to a cloudy mixture (g56°C). With the increase of pH, the gel-to-sol transition (T gelÀsol ) and the clouding temperature (T clouding ) of the sample shifted to higher values, while the sol-to-gel transition temperature (T solÀgel ) remained the same. These transitions and the tunability of T gelÀsol...

We report on the synthesis of thermo-and enzyme-responsive hydrophilic ABA triblock copolymers, poly(ethoxydi(ethylene glycol) acrylate-co-4-((dihydroxyphosphoryl)oxy)butyl acrylate)-b-poly(ethylene oxide)-b-poly(ethoxydi(ethylene glycol) acrylate-co-4-((dihydroxyphosphoryl)oxy)butyl acrylate) (P(DEGEAco-OPBA)-b-PEO-b-P(DEGEA-co-OPBA)), and the enzyme-induced formation of thermoreversible micellar gels from their moderately concentrated aqueous solutions at 37 °C. PDEGEA is a thermosensitive water-soluble polymer with a lower critical solution temperature (LCST) at 9 °C in water. The block copolymers were prepared by atom transfer radical polymerization of DEGEA and 4-((di-tert-butoxyphosphoryl)oxy)butyl acrylate and subsequent removal of tert-butyl groups. To seek optimal conditions for enzymatic gelation of aqueous solutions of triblock copolymers, a study of dephosphorylation of a random copolymer P(DEGEA-co-OPBA) by acid phosphatase in water at 37 °C was carried out. The time for the solution to turn cloudy was found to decrease with the decrease of pH from 5.48 to 4.70 and level off from pH 4.39 to 4.23. The cleavage of phosphate groups made the polymer less hydrophilic and decreased the LCST from above to below 37 °C. Therefore, pH 4.4 was selected to conduct the enzyme-induced gelation of 7.9 wt % aqueous solutions of P(DEGEA-co-OPBA)-b-PEO-b-P(DEGEA-co-OPBA). The gelation processes were monitored by rheological measurements; the solÀgel transition temperature decreased and the gel strength increased with the increase of reaction time. The gels formed were thermoreversible; lowering temperature converted the gels to free-flowing liquids. From 1 H and 31 P NMR spectroscopy analysis, the degree of dephosphorylation was high. The formation of three-dimensional micellar network gels stemmed from the thermosensitive properties of the resultant dephosphorylated triblock copolymers, which was confirmed by a dynamic light scattering study. At a slightly higher pH (4.67), the enzyme-induced gelation was significantly slower, consistent with the observation of the effect of pH on dephosphorylation of the random copolymer by acid phosphatase.

This Article reports on the synthesis of a series of well-defined, tertiary-amine-containing ABA triblock copolymers, composed of a poly(ethylene oxide) (PEO) central block and thermo- and pH-sensitive outer blocks, and the study of the effect of different tertiary amines on thermally induced sol-gel transition temperatures (T(sol-gel)) of their 10 wt % aqueous solutions. The doubly responsive ABA triblock copolymers were prepared from a difunctional PEO macroinitiator by atom transfer radical polymerization of methoxydi(ethylene glycol) methacrylate and ethoxydi(ethylene glycol) methacrylate at a feed molar ratio of 30:70 with ∼5 mol % of either N,N-diethylaminoethyl methacrylate (DEAEMA), N,N-diisopropylaminoethyl methacrylate, or N,N-di(n-butyl)aminoethyl methacrylate. The chain lengths of thermosensitive outer blocks and the molar contents of tertiary amines were very similar for all copolymers. Using rheological measurements, we determined the pH dependences of T(sol-gel) of 10 wt % aqueous solutions of these copolymers in a phosphate buffer. The T(sol-gel) versus pH curves of all polymers exhibited a sigmoidal shape. The T(sol-gel) increased with decreasing pH; the changes were small on both high and low pH sides. At a specific pH, the T(sol-gel) decreased with increasing the hydrophobicity of the tertiary amine, and upon decreasing pH the onset pH value for the T(sol-gel) to begin to increase noticeably was lower for the more hydrophobic tertiary amine-containing copolymer. In addition, we studied the effect of different tertiary amines on the release behavior of FITC-dextran from 10 wt % micellar gels in an acidic medium at 37 and 27 °C. The release profiles for three studied hydrogels at 37 °C were essentially the same, suggesting that the release was dominated by the diffusion of FITC-dextran. At 27 °C, the release was significantly faster for the DEAEMA-containing copolymer, indicating that both diffusion and gel dissolution contributed to the release at this temperature.

Polymer composites are found throughout the world both natural and artificial in origin. In the vast majority of applications, composites serve as structural support or reinforcement roles. Demand for lightweight tough composites is growing in multiple application spaces such as areospace, biomaterials, and infrastructure with physical properties as diverse as the applications. The unifying component in all composites is the presence of an interphase. Many measurement techniques and measurement tools have been developed for the study of this crucial region in composite materials. Many of these methods are great for the measurment and study of bulk properties or model systems. However, development of methods that permit the direct observation of interactions at the interphase during applied stress are needed. Here we employ fluorescence lifetime imaging and hyperspectral imaging to observe activation of a fluorogenic dye at the composite interface as a result of applied stress. The advantages of this sytem include commercial availability of the dye precursor, and simple one‐pot functionalization. The attachment of the dye at the interface is easily monitored through emission wavelength shifts and fluorescence lifetime variations. Interfacial mechano‐responsive dyes have potential for both fundamental studies as well as industrial use as a structural health monitoring tool.