Broad Chiroptical Activity from Ultraviolet to Short-Wave Infrared by Chirality Transfer from Molecular to Micrometer Scale.

Chiral nanomaterials provide a rich platform for versatile applications. Tuning the wavelength of polarization rotation maxima in the broad range including short-wave infrared (SWIR) is a promising candidate for infrared neural stimulation, imaging, and nanothermometry. However, the majority of previously developed chiral nanomaterials reveal the optical activity in a relatively shorter wavelength range (ultraviolet-visible, UV-vis), not in SWIR. Here, we demonstrate a versatile method to synthesize chiral copper sulfides using cysteine, as the stabilizer, and transferring the chirality from molecular- to the microscale through self-assembly. The assembled structures show broad chiroptical activity in the UV-vis-NIR-SWIR region (200-2500 nm). Importantly, we can tune the chiroptical activity by simply changing the reaction conditions. This approach can be extended to materials platforms for developing next-generation optical devices, metamaterials, telecommunications, and asymmetric catalysts.

Chiral Supraparticles for Controllable Nanomedicine.

Chirality is ubiquitous in nature and hard-wired into every biological system. Despite the prevalence of chirality in biological systems, controlling biomaterial chirality to influence interactions with cells has only recently been explored. Chiral-engineered supraparticles (SPs) that interact differentially with cells and proteins depending on their handedness are presented. SPs coordinated with d-chirality demonstrate greater than threefold enhanced cell membrane penetration in breast, cervical, and multiple myeloma cancer cells. Quartz crystal microbalance with dissipation and isothermal titration calorimetry measurements reveal the mechanism of these chiral-specific interactions. Thermodynamically, d-SPs show more stable adhesion to lipid layers composed of phospholipids and cholesterol compared to l-SPs. In vivo, d-SPs exhibit superior stability and longer biological half-lives likely due to opposite chirality and thus protection from endogenous proteins including proteases. This work shows that incorporating d-chirality into nanosystems enhances uptake by cancer cells and prolonged in vivo stability in circulation, providing support for the importance of chirality in biomaterials. Thus, chiral nanosystems may have the potential to provide a new level of control for drug delivery systems, tumor detection markers, biosensors, and other biomaterial-based devices.