Here, we report the mechanisms of chiral transfer at various length scales in the self-assembly of enantiomeric chiral block copolymers (BCPs*). We show the evolution of homochirality from molecular chirality into phase chirality in the self-assembly of the BCPs*. The chirality of the molecule in the BCP* is identified from circular dichroism (CD) spectra, while the handedness of the helical conformation in the BCP* is determined from a split-type Cotton effect in vibrational circular dichroism spectra. Microphase separation of the BCP* is exploited to form a helical (H*) phase, and the handedness of helical nanostructure in the BCP* is directly visualized from transmission electron microscopy tomography. As examined by CD and fluorescence experiments, significant induced CD signals and a bathochromic shift of fluorescence emission for the achiral perylene moiety as a chemical junction of the BCPs* can be found while the concentration of the BCPs* in toluene solution is higher than the critical micelle concentration, suggesting a twisting and shifting mechanism initiating from the microphase-separated interface of the BCPs* leading to formation of the H* phase from self-assembly.

We describe microstructural aspects of phase transitions between the lamellar (L), perforated layer (PL), and gyroid (G) morphologies in diblock copolymer melts. Using small-angle scattering, dynamic mechanical spectroscopy, and transmission electron microscopy, we show that these transformations proceed through the nucleation and growth of the final phase, in contrast to recent calculations that assume evolution from a thermodynamically unstable initial state. Direct L → G transitions are suppressed by the high surface tension associated with L−G grain boundaries; the formation of the metastable PL structure under such conditions reflects the ease with which the L → PL transition can occur, compared to L → G. Similar effects dominate the G → L transition. Mismatches in spacings between epitaxially related lattice planes also influence relaxation kinetics; the P → LG transition rate depends strongly on the relative spacings of the PL [10] and G [211] planes, and the considerable discrepancy between the G [211] and L [10] spacings at the L−G boundary may further retard that transformation. Similar factors have been shown to govern the evolution of amphiphilic systems, supporting geometrically inspired attempts to understand this phase behavior.

A series of semicrystalline block copolymers, poly(4-vinylpyridine)-block-poly(ε-caprolactone) (P4VP−PCL), with lamellar microstructure have been synthesized. Owing to the vitrified P4VP microdomains and strongly segregated microphase separation, the crystallization of the PCL blocks in P4VP−PCL was carried out within the nanoscale confinement. Simply by varying the molecular weight of the block copolymer, namely the confined size, polymeric crystallization can be tailored in the one-dimensional confinement. A distinct nucleation mechanism, altering from heterogeneous to homogeneous nucleation, was obtained once the confined size became smaller than a critical dimension, equivalent to the regular thickness of heterogeneously nucleated crystalline lamellae. Consequently, discrete crystalline granules were generated through homogeneous nucleation, namely a single nucleus within one granule. Also, crystal growth was altered from specific to random orientation with respect to the interface between the crystalline and amorphous domains in the copolymers. This system thus serves as a model to analyze the impact of confined size in 1D spatial confinement on the crystallization of polymers.

A novel method using a temperature-sensitive polymer (methylcellulose) to thermally gel aqueous alginate blended with distinct salts (CaCl2, Na2HPO4, or NaCl), as a pH-sensitive hydrogel was developed for protein drug delivery. It was noted that the salts blended in hydrogels may affect the structures of an entangled network of methylcellulose and alginate and have an effect on their swelling characteristics. The methylcellulose/alginate hydrogel blended with 0.7 M NaCl (with a gelation temperature of 32 degrees C) demonstrated excellent pH sensitivity and was selected for the study of release profiles of a model protein drug (bovine serum albumin, BSA). In the preparation of drug-loaded hydrogels, BSA was well-mixed to the dissolved aqueous methylcellulose/alginate blended with salts at 4 degrees C and then gelled by elevating the temperature to 37 degrees C. This drug-loading procedure in aqueous environment at low temperature may minimize degradation of the protein drug while achieving a high loading efficiency (95-98%). The amount of BSA released from test hydrogels was a function of the amount of alginate used in the hydrogels. The amount of BSA released at pH 1.2 from the test hydrogel with 2.5% alginate was relatively low (20%), while that released at pH 7.4 increased significantly (86%). In conclusion, the methylcellulose/alginate hydrogel blended with NaCl could be a suitable carrier for site-specific protein drug delivery in the intestine.

The significance of chirality transfer is not only involved in biological systems, such as the origin of homochiral structures in life but also in man-made chemicals and materials. How the chiral bias transfers from molecular level (molecular chirality) to helical chain (conformational chirality) and then to helical superstructure or phase (hierarchical chirality) from self-assembly is vital for the chemical and biological processes in nature, such as communication, replication, and enzyme catalysis. In this Account, we summarize the methodologies for the examination of homochiral evolution at different length scales based on our recent studies with respect to the self-assembly of chiral polymers and chiral block copolymers (BCPs*). A helical (H*) phase to distinguish its P622 symmetry from that of normal hexagonally packed cylinder phase was discovered in the self-assembly of BCPs* due to the chirality effect on BCP self-assembly. Enantiomeric polylactide-containing BCPs*, polystyrene-b-poly(l-lactide) (PS-PLLA) and polystyrene-b-poly(d-lactide) (PS-PDLA), were synthesized for the examination of homochiral evolution. The optical activity (molecular chirality) of constituted chiral repeating unit in the chiral polylactide is detected by electronic circular dichroism (ECD) whereas the conformational chirality of helical polylactide chain can be explicitly determined by vibrational circular dichroism (VCD). The H* phases of the self-assembled polylactide-containing BCPs* can be directly visualized by 3D transmission electron microscopy (3D TEM) technique at which the handedness (hierarchical chirality) of the helical nanostructure is thus determined. The results from the ECD, VCD, and 3D TEM for the investigated chirality at different length scales suggest the homochiral evolution in the self-assembly of the BCPs*. For chiral polylactides, twisted lamellae in crystalline banded spherulite can be formed by dense packing scheme and effective interactions upon helical chains from self-assembly. The handedness of the twisted lamella can be determined by using rotation experiment of polarized light microscopy (PLM). Similar to the self-assembly of BCPs*, the examined results suggest the homochiral evolution in the crystallized chiral polylactides. The results presented in this Account demonstrate the notable progress in the spectral and morphological determination for the examination of molecular, conformational, and hierarchical chirality in self-assembled twisted superstructures of chiral polymers and helical phases of block copolymers and suggest the attainability of homochiral evolution in the self-assembly of chiral homopolymers and BCPs*. The suggested methodologies for the understanding of the mechanisms of the chirality transfer at different length scales provide the approaches to give Supporting Information for disclosing the mysteries of the homochiral evolution from molecular level.

We report a kinetic study of Ag nanoparticles (AgNPs) under acidic environments (i.e., pH 2.3 to pH ≈7) and systematically investigate the impact of protein interactions [i.e., bovine serum albumin (BSA) as representative] to the colloidal stability of AgNPs. Electrospray-differential mobility analysis (ES-DMA) was used to characterize the particle size distributions and the number concentrations of AgNPs. Transmission electron microscopy was employed orthogonally to provide visualization of AgNPs. For unconjugated AgNPs, the extent of aggregation, or the average particle size, was shown to be increased significantly with an increase of acidity, where a partial coalescence was found between the primary particles of unconjugated AgNP clusters. Aggregation rate constant, kD, was also shown to be proportional to acidity, following a correlation of log(kD) = -1.627(pH)-9.3715. Using ES-DMA, we observe BSA had a strong binding affinity (equilibrium binding constant, ≈ 1.1 × 10(6) L/mol) to the surface of AgNPs, with an estimated maximum molecular surface density of ≈0.012 nm(-2). BSA-functionalized AgNPs exhibited highly-improved colloidal stability compared to the unconjugated AgNPs under acidic environments, where both the acid-induced interfacial dissolution and the particle aggregation became negligible. Results confirm a complex mechanism of colloidal stability of AgNPs: the aggregation process was shown to be dominant, and the formation of BSA corona on AgNPs suppressed both particle aggregation and interfacial dissolution of AgNP samples under acidic environments.

A simple method for the preparation of nanomaterials with new functionality by physical displacement of a network phase is suggested, giving a change in space group symmetry and hence properties. A double gyroid structure made by the self-assembly of block copolymers is used as a model system for the demonstration of shifting networks to achieve single gyroid-like scattering properties. Free-standing single gyroid-like network materials can be fabricated to give nanophotonic properties, similar to the photonic properties of a butterfly wing structure.

In this study, a novel perovskite quantum dot (QD) spray-synthesis method is developed by combining traditional perovskite QD synthesis with the technique of spray pyrolysis. By utilizing this new technique, the synthesis of cubic-shaped perovskite QDs with a homogeneous size of 14 nm is demonstrated, which shows an unprecedented stable absolute photoluminescence quantum yield ≈100% in the solution and even in the solid-state neat film. The highly emissive thin films are integrated with light emission devices (LEDs) and organic light emission displays (OLEDs). The color conversion type QD-LED (ccQD-LED) hybrid devices exhibit an extremely saturated green emission, excellent external quantum efficiency of 28.1%, power efficiency of 121 lm W , and extraordinary forward-direction luminescence of 8 500 000 cd m . The conceptual ccQD-OLED hybrid display also successfully demonstrates high-definition still images and moving pictures with a 119% National Television System Committee 1931 color gamut and 123% Digital Cinema Initiatives-P3 color gamut. These very-stable, ultra-bright perovskite QDs have the properties necessary for a variety of useful applications in optoelectronics.