Emulsion Solvent Evaporation-Induced Self-Assembly of Block Copolymers Containing pH-Sensitive Block

A simple yet efficient method is developed to manipulate the self-assembly of pH-sensitive block copolymers (BCPs) confined in emulsion droplets. Addition of acid induces significant variation in morphological transition (e.g., structure and surface composition changes) of the polystyrene-<i>block</i>-poly­(4-vinylpyridine) (PS-<i>b</i>-P4VP) assemblies, due to the hydrophobic–hydrophilic transition of the pH-sensitive P4VP block via protonation. In the case of pH > p<i>K</i>a_(P4VP) (p<i>K</i>a _(P4VP) = 4.8), the BCPs can self-assemble into pupa-like particles because of the nearly neutral wetting of PS and P4VP blocks at the oil/water interface. As expected, onion-like particles obtained when pH is slightly lower than p<i>K</i>a_(P4VP) (e.g., pH = 3.00), due to the interfacial affinity to the weakly hydrophilic P4VP block. Interestingly, when pH was further decreased to ∼2.5, interfacial instability of the emulsion droplets was observed, and each emulsion droplet generated nanoscale assemblies including vesicles, worm-like and/or spherical micelles rather than a nanostructured microparticle. Furthermore, homopolymer with different molecular weights and addition ratio are employed to adjust the interactions among copolymer blocks. By this means, particles with hierarchical structures can be obtained. Moreover, owing to the kinetically controlled processing, we found that temperature and stirring speed, which can significantly affect the kinetics of the evaporation of organic solvent and the formation of particles, played a key role in the morphology of the assemblies. We believe that manipulation of the property for the aqueous phase is a promising strategy to rationally design and fabricate polymeric assemblies with desirable shapes and internal structures

Dependence of Melt Behavior of Star Polystyrene/POSS Composites on the Molecular Weight of Arm Chains

Rheological behavior of three-arm and six-arm star polystyrene (SPS) with a small amount of polyhedral oligosilsesquioxane (POSS) was studied. Both linear oscillatory frequency sweep and steady state shear results of SPS/POSS composites showed the reduction of melt viscosity in the unentangled SPS matrix and the increase of viscosity in the entangled SPS matrix. In particular, when molecular weight of the arm (<i>M</i>_a) of SPS was smaller than the critical molecular weight for entanglement (<i>M</i>_c) of PS, the melt viscosity of SPS/POSS composites with low content of POSS was lower than that of pure SPS. The abnormal phenomenon of reduced melt viscosity in SPS/POSS composites was in coincidence with the melt viscosity behavior of SPS/C₆₀ composites reported in our previous work (Soft Matter 2013, 9, 6282−6290), although the diameters of two nanoparticles and their interaction with SPS matrix were different. A possible mechanism behind the melt viscosity behavior was discussed. Furthermore, the time–temperature superposition principle (TTS) was applied in SPS and SPS/POSS composites. The Cox–Merz empirical relationship was verified to be valid for SPS/POSS composites when the content of POSS was low (1 wt %)

Responsive Photonic Hydrogel-Based Colorimetric Sensors for Detection of Aldehydes in Aqueous Solution

In this work, we present a fast and efficient strategy for the preparation of responsive photonic hydrogels for aldehyde sensing by combining the self-assembly of monodisperse carbon-encapsulated Fe₃O₄ nanoparticles (NPs) and in situ photopolymerization of polyacrylamide (PAM) hydrogels. The responsive photonic hydrogels exhibit structural color variation after being treated with formaldehyde aqueous solution, which can be attributed to the chemical reaction between the amide groups in the hydrogels and the formaldehyde. We have also shown that the photonic hydrogels can be used to determine the concentration of formaldehyde and to differentiate aldehydes through a facile reflection spectra shift and color change. This study provides a facile strategy for the visualized determination of aldehyde in aqueous solution

Nanostructure and Linear Rheological Response of Comb-like Copolymer PSVS‑<i>g</i>‑PE Melts: Influences of Branching Densities and Branching Chain Length

Comb-like poly­(styrene-<i>co</i>-4-(vinylphenyl)-1-butene)-<i>g</i>-polyethylene copolymers (PSVS-<i>g</i>-PE) with various branching parameters were synthesized to study the influence of branch chains on morphology (at melt state) and linear rheological response of the copolymers. The results showed that both the branching density and branch chain length of PSVS-<i>g</i>-PE copolymers strongly affected linear rheological behavior of the copolymers, resulting from the formation of different microphase separation structure in the melt state. PSVS-<i>g</i>-PE copolymers with low branching density (2.3–3.5 branch chains per 100 repeating units of the backbone) showed a microphase-separated structure at the melt state, and a typical rheological characteristic for network-like structure was observed. Furthermore, the type of microphase-separated structure at the melt state strongly influences the applicability of the time–temperature superposition (TTS) principle. As a result, the TTS failure was observed in the modulus curves for PSVS52.7-3.5-PE4.9 (poor-order lamellar structure) and PSVS54.4-2.7-PE10.7 (long tubular structure). In contrast, the PSVS-<i>g</i>-PE sample with high branching density (16.6–24.5 branch chains per 100 repeating units of the backbone) showed homogeneous phase structure and normal rheological behavior, similar to linear or comb-like homopolymers. The gel-like state appeared in a limited frequency regime (a plateau regime of tan δ versus ω) during decreasing the frequency from the high frequency regime in these comb-like copolymers