The concept of the “supramolecular photothermal effects” refers to the collection property and photothermal conversion efficiency resulting from the supramolecular assembly of molecular photothermal sensitizers. This review considers organic supramolecular photothermal materials assembled at the nanoscale via various molecular self‐assembly strategies and associated with the organization of multiple noncovalent interactions. In these materials, the individual photosensitizer molecules are typically aggregated through self‐assembly in a certain form that exhibits enhanced biostability, increased photothermal conversion efficiency with photoluminescence quenching, and improved photothermal therapeutic effects in comparison with those of the monomeric photosensitizer molecules. These supramolecular photothermal effects are controlled or influenced by intermolecular noncovalent interactions, especially the hydrophobic effects, which are distinct from the mechanisms of conventional sensitizer molecules and polymers and inorganic photothermal agents. A focus lies on how self‐assembly strategies give rise to supramolecular photothermal effects, including polymer and protein fabrication, small molecule self‐assembly, and the construction of donor–acceptor binary systems. Emphases are placed on the rational design of supramolecular photothermal nanomaterials, drug delivery, and in vivo photothermal therapeutic effects. Finally, the key challenges and promising prospects of these supramolecular photothermal nanomaterials in terms of both technical advances and clinical translation are discussed.

Photothermal nanomaterials that integrate multimodal imaging and therapeutic functions provide promising opportunities for noninvasive and targeted diagnosis and treatment in precision medicine. However, the clinical translation of existing photothermal nanoagents is severely hindered by their unclear physiological metabolism, which makes them a strong concern for biosafety. Here, the utilization of biliverdin (BV), an endogenic near‐infrared (NIR)‐absorbing pigment with well‐studied metabolic pathways, to develop photothermal nanoagents with the aim of providing efficient and metabolizable candidates for tumor diagnosis and therapy, is demonstrated. It is shown that BV nanoagents with intense NIR absorption, long‐term photostability and colloidal stability, and high photothermal conversion efficiency can be readily constructed by the supramolecular multicomponent self‐assembly of BV, metal‐binding short peptides, and metal ions through the reciprocity and synergy of coordination and multiple noncovalent interactions. In vivo data reveal that the BV nanoagents selectively accumulate in tumors, locally elevate tumor temperature under mild NIR irradiation, and consequently induce efficient photothermal tumor ablation with promising biocompatibility. Furthermore, the BV nanoagents can serve as a multimodal contrast for tumor visualization through both photoacoustic and magnetic resonance imaging. BV has no biosafety concerns, and thereby offers a great potential in precision medicine by integrating multiple theranostic functions.

Inspired by the dynamic morphology control of molecular assemblies in biological systems,wehave developed pH-responsive transformable peptide-based nanoparticles for photodynamic therapy(PDT) with prolonged tumor retention times.T he self-assembled peptide-porphyrin nanoparticles transformed into nanofibers when exposed to the acidic tumor microenvironment, which was mainly driven by enhanced intermolecular hydrogen bond formation between the protonated molecules.T he nanoparticle transformation into fibrils improved their singlet oxygen generation ability and enabled high accumulation and long-term retention at tumor sites. Strong fluorescent signals of these nanomaterials were detected in tumor tissue up to 7daysafter administration. Moreover,the peptide assemblies exhibited excellent anti-tumor efficacy via PDT in vivo.This in situ fibrillar transformation strategy could be utilized to design effective stimuli-responsive biomaterials for long-term imaging and therapy.

The presumed ground state of a nematic fluid confined in a cylindrical geometry with planar anchoring corresponds to that of an axial configuration, wherein the director, free of deformations, is along the long axis of the cylinder. However, upon confinement of lyotropic chromonic liquid crystals in cylindrical geometries, here we uncover a surprising ground state corresponding to a doubly twisted director configuration. The stability of this ground state, which involves significant director deformations, can be rationalized by the saddle-splay contribution to the free energy. We show that sufficient anisotropy in the elastic constants drives the transition from a deformation-free ground state to a doubly twisted structure, and results in spontaneous symmetry breaking with equal probability for either handedness. Enabled by the twist angle measurements of the spontaneous twist, we determine the saddle-splay elastic constant for chromonic liquid crystals for the first time.

Experimental details, synthesis and analysis of the monomers and polymers, additional figures, and additional characterization data (PDF).