Supramolecular nanomedicines, which use supramolecular design to improve the precision and effectiveness of pharmaceutical practice and optimize pharmacokinetic profiles, have gathered momentum to battle cancer and other incurable diseases, for which traditional small‐molecular and macromolecular drugs are less effective. However, the lack of clinical approval of supramolecular assembly‐based medicine underscores the challenges facing this field. A 2D nanodisc‐based supramolecular structure is formed by a non‐ionic heptamethine cyanine (Cy7) dye, which generates fluorescence self‐quenching but unique photothermal and photoacoustic properties. These Cy7‐based supramolecular nanodiscs exhibit passive tumor‐targeting properties to not only visualize the tumor by near‐infrared fluorescence imaging and photoacoustic tomography but also induce photothermal tumor ablation under irradiation. Due to the nature of organic small molecule, they induce undetectable acute toxicity in mice and can be eliminated by the liver without extrahepatic metabolism. These findings suggest that the self‐assembling cyanine discs represent a new paradigm in drug delivery as single‐component supramolecular nanomedicines that are self‐delivering and self‐formulating, and provide a platform technology for synergistic clinical cancer imaging and therapy.
Organic small-molecule-based
photothermal agents such as cyanine
dyes have received increasing attention in developing novel cancer
therapies with potential clinical utility but suffer from poor stability,
low photothermal efficiency, and limited accumulation at tumor sites
in molecular forms. Self-assembly of small-molecule dyes into supramolecular
assemblies may address these concerns by controlling the molecular
organization of dye monomers to form structures of a higher order.
Among them, H-aggregates of dyes favor face-to-face contacts with
strongly overlapping areas, which always have a negative connotation
to exhibit low or no fluorescence in most cases but may emanate energy
in nonradiative forms such as heat for photothermal cancer therapy
applications. Here, the synergistic self-assembly of cyanine dyes
into H-aggregates is developed as a new supramolecular strategy to
fabricate small-molecule-based photothermal nanomaterials. Compared
to the free cyanine dyes, the H-aggregates assembled from pyrene or
tetraphenylethene (TPE) conjugating cyanine exhibit the expected absorption
spectral blue shift and fluorescence self-quenching but unique photothermal
properties. Remarkably, the obtained H-aggregates are saucer-shaped
nanoparticles that exhibit passive tumor-targeting properties to induce
imaging-guided photothermal tumor ablation under irradiation. This
supramolecular strategy presented herein may open up new opportunities
for constructing next-generation small-molecule-based self-assembly
nanomaterials for PTT cancer therapy in clinics.
The stability of supported liquid membranes (SLMs) was partially improved by using a room-temperature ionic liquid (RTIL) as the membrane liquid and by employing a vapor permeation process for the separation of toluene/cyclohexane systems and the dehydration of aqueous 1-propanol and aqueous ethanol mixtures. Because the basic characteristics of RTILs are that they have high surface tension and no detectable vapor pressure, the loss of membrane liquid by evaporation was avoided completely. The separation of toluene/ cyclohexane mixtures was conducted for as long as 550 h, and the separation factor was kept within the range of 15-25, with the membrane showing good durability in vapor permeation. The use of SLMs with ionic liquids was shown to be a promising method for separating organic/organic and organic/water mixtures.
Polythiophene nanoparticles with large TPA cross section and high1O2generation quantum yield have been developed for simultaneous lysosome-targetable fluorescence imaging and photodynamic therapy.
Owing to the intrinsic advantages of spatiotemporal selectivity, photothermal theranostics have become the advancing edge of precision medicine for cancer. Developing photothermal transduction agents (PTAs) with near‐infrared (NIR) absorption, high photothermal conversion efficiency, robust photothermal stability, and good accumulation in tumors, is particularly valuable. Herein, we report a new concept, self‐assembly‐induced crystallization (SAIC), which can serve as a mechanism that dramatically boosts photothermal behaviors of PTA in NIR region. As a proof of concept, three heptamethine cyanine molecules with internal degrees of freedom (geometry and intramolecular interaction) are designed to fine‐tune their crystallinity. Notably, Cy7‐TCF‐EMBI molecules with rigid and planar skeletons self‐assemble into a crystalline state to maximize their packing density and improve the charge transfer, both of which contribute to nonradiative decay for energy dissipation as heat. The high packing density also renders an ideal scaffold for controlling intermolecular interactions to exhibit better photothermal stability, and endows an anisotropic three‐dimensional architecture for passive tumor targeting. This “SAIC” strategy may offer a conceptually novel, practically simple but effective approach to unveil the structure–property relationship that could provide some general rules in rational design of PTAs, and paves the way for a next generation of supramolecular medicine for photothermal theranostics.
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