Herein, we report a simple and robust strategy for preparing dual-responsive shape-switchable block copolymer (BCP) particles, which respond to subtle temperature and pH changes near physiological conditions (i.e., human body temperature and neutral pH). The shape transition of polystyrene-b-poly(4-vinylpyridine) BCP particles between lens and football shapes occurs in very narrow temperature and pH ranges: no temperature-based transition for pH 6.0, 40−50 °C transition for pH 6.5, and 25−35 °C for pH 7.0. To achieve these shape transitions, temperature/pH-responsive polymer surfactants of poly(N-(2-(diethylamino)ethyl)acrylamide-r-N-isopropylacrylamide) are designed to induce dramatic changes in relative solubility and their location in response to temperature and pH changes near physiological conditions. In addition, the BCP particles exhibit reversible shapetransforming behavior according to orthogonal temperature and pH changes. Colorimetric measurements of temperature and pH changes are enabled by shape-transforming properties combined with selective positioning of dyes, suggesting promising potential for these particles in clinical and biomedical applications.

We examined the packing structure of polystyrene-coated gold nanoparticles (Au@PS) as a function of grafting density. A series of Au@PS nanoparticles with grafting densities in the range of 0.51−1.94 chains nm −2 were prepared by a ligand exchange process using thiol-terminated PS and then selfassembled at a liquid−air interface. We observed a transition from disordered to bodycentered cubic (bcc) to face-centered cubic (fcc) arrangements with increasing grafting density, even though the ligand length-to-core radius ratio (λ) was as high as 3.0, a condition that typically favors nonclose-packed bcc symmetry in the self-assembly of hard nanoparticles. To explain this phenomenon, we define λ eff to include the concentrated polymer brush regime as part of the "hard core", which predicts that the softness of Au@PS nanoparticles is reduced from 1.53 to 0.14 in a theta solvent as the grafting density increases from 0.51 to 1.94 chains nm −2 . This new definition of λ can also predict the effective radii of nanoparticles using the established optimal packing model. The experimental findings are supported by a combination of coarse-grained molecular dynamics simulation and adaptive common neighbor analysis, which show that changes in grafting density can drive the observed transitions in nanoparticle packing. These studies provide new insights for controlling the selfassembled symmetries of polymer-coated nanocrystals using a simple ligand exchange process to tune particle softness.

Development of particles that change shape in response to external stimuli has been a long-thought goal for producing bioinspired, smart materials. Herein, the temperature-driven transformation of the shape and morphology of polymer particles composed of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymers (BCPs) and temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) surfactants is reported. PNIPAM acts as a temperature-responsive surfactant with two important roles. First, PNIPAM stabilizes oil-in-water droplets as a P4VP-selective surfactant, creating a nearly neutral interface between the PS and P4VP domains together with cetyltrimethylammonium bromide, a PS-selective surfactant, to form anisotropic PS-b-P4VP particles (i.e., convex lenses and ellipsoids). More importantly, the temperature-directed positioning of PNIPAM depending on its solubility determines the overall particle shape. Ellipsoidal particles are produced above the critical temperature, whereas convex lens-shaped particles are obtained below the critical temperature. Interestingly, given that the temperature at which particle shape change occurs depends solely on the lower critical solution temperature (LCST) of the polymer surfactants, facile tuning of the transition temperature is realized by employing other PNIPAM derivatives with different LCSTs. Furthermore, reversible transformations between different shapes of PS-b-P4VP particles are successfully demonstrated using a solvent-adsorption annealing with chloroform, suggesting great promise of these particles for sensing, smart coating, and drug delivery applications.

Surface-engineered, 10 nm-sized graphene quantum dots (GQDs) are shown to be efficient surfactants for producing 3-pentadecyl phenol (PDP)-combined poly­(styrene-b-4-vinylpyridine) (PS-b-P4VP­(PDP)) particles that feature tunable shapes and internal morphologies. The surface properties of GQDs were modified by grafting different alkyl ligands, such as hexylamine and oleylamine, to generate the surfactant behavior of the GQDs. In stark contrast to the behavior of the unmodified GQDs, hexylamine-grafted GQDs and oleylamine-grafted GQD surfactants were selectively positioned on the PS and P4VP­(PDP) domains, respectively, at the surface of the particles. This positioning effectively tuned the interfacial interaction between two different PS/P4VP­(PDP) domains of the particles and the surrounding water during emulsification and induced a dramatic morphological transition to convex lens-shaped particles. Precise and systematic control of interfacial activity of GQD surfactants was also demonstrated by varying the density of the alkyl ligands on the GQDs. The excellent surface tunability of 10 nm-sized GQDs combined with their significant optical and electrical properties highlight their importance as surfactants for producing colloidal particles with novel functions.

Highly-selective optical sensors that are capable of detecting complex stimuli have attracted significant interest in environmental, biomedical, and analytical chemistry applications. In this work, we report the development of novel and versatile platform for highly-efficient, colorimetric multi-functional sensors using block copolymer-integrated graphene quantum dots (bcp-GQDs). In particular, the multi-functional sensing behavior is successfully generated simply by grafting blue emitting, temperature-responsive block copolymers onto greenemitting, 10-nm size GQD with the GQD providing luminescent response to pH changes. Thus, the bcp-GQDs showed simultaneous, orthogonal sensing behavior to temperature and pH, as well as dose-dependent responses to different types of metal ions. In addition, the bcp-GQD sensor showed excellent reversibility and dispersion stability in pure water, indicating that our system is an ideal platform for environmental and biological applications. The detailed mechanism of the responsive behavior of the bcp-GQDs was elucidated by measurements of time-resolved fluorescence and dynamic light scattering.