New approach for SANS measurement of micelle chain mixing during size and morphology transitions.

Chain exchange in amphiphilic block polymer micelles is measurable with time-resolved small-angle neutron scattering (TR-SANS) where contrast-matched conditions reveal chain mixing as reduced intensity. However, analyzing chain mixing on short time scales e.g. during micelle transformations remains challenging. SANS model fitting can quantify chain mixing during size and morphology changes, however short acquisition times lead to lower data statistics (higher error). Such data are unsuitable for form factor fitting, especially with polydisperse and/or multimodal scenarios. An integrated-reference approach, R(t), is compatible with such data by using fixed reference patterns for the unmixed and fully mixed states that are each integrated to improve data statistics (lower error). Although the R(t) approach is tolerant of low data statistics, it remains incompatible with size and morphology changes. A new shifting references relaxation approach, SRR(t), is proposed where reference patterns are acquired at each time point to enable mixed state calculations regardless of short acquisition times. The additional experimental measurements needed are described which provide these time-varying reference patterns. The use of reference patterns makes the SRR(t) approach size/morphology-agnostic, allowing for the extent of micelle mixing to be directly calculated without this knowledge. SRR(t) is thus compatible with arbitrary levels of complexity and can provide accurate assessment of the mixed state which could support future model analysis. Calculated scattering datasets were used to demonstrate the SRR(t) approach during multiple size, morphology, and solvent conditions (scenarios 1-3). The mixed state calculated from the SRR(t) approach is shown to be accurate for all three scenarios.

Coordination of Quantum Dots in a Polar Solvent by Small-Molecule Imidazole Ligands.

Colloidal quantum dots (QDs) are attractive fluorophores for bioimaging and biomedical applications because of their favorable and tunable optoelectronic properties. In this study, the native hydrophobic ligand environment of oleate-capped sphalerite CdSe/ZnS core/shell QDs was quantitatively exchanged with a set of imidazole-bearing small-molecule ligands. Inductively coupled plasma-optical emission spectroscopy and 1H NMR were used to identify and quantify three different ligand exchange processes: Z-type dissociation of the Zn(oleate)2, L-type association of the imidazole, and X-type anionic exchange of oleate with Cl-, all of which contributed to the overall ligand exchange.

Persistent Micelle Corona Chemistry Enables Constant Micelle Core Size with Independent Control of Functionality and Polyelectrolyte Response.

Polymer micelles have found significant uses in areas such as drug/gene delivery, medical imaging, and as templates for nanomaterials. For many of these applications, the micelle performance depends on its size and chemical functionalization. To date, however, these parameters have often been fundamentally coupled since the equilibrium size of a micelle is a function of the chemical composition in addition to other parameters. Here, we demonstrate a novel processing pathway allowing for the chemical modification to the corona of kinetically trapped "persistent" polymer micelles, termed Persistent Micelle Corona Chemistry (PMCC). Judicious planning is crucial to this size-controlled functionalization where each step requires all reagents and polymer blocks to be compatible with (1) the desired chemistry, (2) micelle persistency, and (3) micelle dispersion. A desired functionalization can be implemented with PMCC by pairing the synthetic planning with polymer solubility databases. Specifically, poly(cyclohexyl methacrylate-b-(diethoxyphosphoryl)methyl methacrylate) (PCHMA-b-PDEPMMA) was prepared to combine a glassy-core block (PCHMA) for kinetic control with a block (PDEPMMA) that is able to be hydrolyzed to yield acid groups. The processing sequence determines the resulting micelle size distribution where the hydrolyzed-then-micellized sequence yields widely varying micelle dimensions due to equilibration. In contrast, the micellized-then-hydrolyzed sequence maintains kinetically trapped micelles throughout the PMCC process. Statistically significant transmission electron microscopy (TEM) measurements demonstrate that PMCC uniquely enables this functionalization with constant average micelle core dimensions. Furthermore, these kinetically trapped micelles also subsequently maintain constant micelle core size when modifying the Coulombic interactions of the micelle corona via pH changes.

One-Pot Self-Assembly of Sequence-Controlled Mesoporous Heterostructures via Structure-Directing Agents.

Multimaterial heterostructures have led to characteristics surpassing the individual components. Nature controls the architecture and placement of multiple materials through biomineralization of nanoparticles (NPs); however, synthetic heterostructure formation remains limited and generally departs from the elegance of self-assembly. Here, a class of block polymer structure-directing agents (SDAs) are developed containing repeat units capable of persistent (covalent) NP interactions that enable the direct fabrication of nanoscale porous heterostructures, where a single material is localized at the pore surface as a continuous layer. This SDA binding motif (design rule 1) enables sequence-controlled heterostructures, where the composition profile and interfaces correspond to the synthetic addition order. This approach is generalized with 5 material sequences using an SDA with only persistent SDA-NP interactions ("P-NP1-NP2"; NPi = TiO2, Nb2O5, ZrO2). Expanding these polymer SDA design guidelines, it is shown that the combination of both persistent and dynamic (noncovalent) SDA-NP interactions ("PD-NP1-NP2") improves the production of uniform interconnected porosity (design rule 2). The resulting competitive binding between two segments of the SDA (P- vs D-) requires additional time for the first NP type (NP1) to reach and covalently attach to the SDA (design rule 3). The combination of these three design rules enables the direct self-assembly of heterostructures that localize a single material at the pore surface while preserving continuous porosity.