Functional Nanomaterials Based on Self‐Assembly of Endogenic NIR‐Absorbing Pigments for Diagnostic and Therapeutic Applications

Endogenic pigments derived from hemoglobin have been successfully applied in the clinic for both imaging and therapy based on their inherent photophysical and photochemical properties, including light absorption, fluorescence emission, and producing reactive oxygen species. However, the clinically approved endogenic pigments can be excited only by UV/vis light, restricting the penetration depth of in vivo applications. Recently, endogenic pigments with NIR‐absorbing properties have been explored for constructing functional nanomaterials. Here, the overview of NIR‐absorbing endogenic pigments, mainly bile pigments, and melanins, as emerging building blocks for supramolecular construction of diagnostic and therapeutic nanomaterials is provided. The endogenic origins, synthetic pathways, and structural characteristics of the NIR‐absorbing endogenic pigments are described. The self‐assembling approaches and noncovalent interactions in fabricating the nanomaterials are emphasized. Since bile pigments and melanins are inherently photothermal agents, the resulting nanomaterials are demonstrated as promising candidates for photoacoustic imaging and photothermal therapy. Integration of additional diagnostic and therapeutic agents by the nanomaterials through chemical conjugation or physical encapsulation toward synergetic effects is also included. Especially, the degradation behaviors of the nanomaterials in biological environments are summarized. Along with the challenges, future perspectives are discussed for accelerating the ration design and clinical translation of NIR‐absorbing nanomaterials. Endogenic pigments are promising photoactive agents for diagnostic and therapeutic applications with the advantages of good biocompatibility and biodegradability. This review summarizes the recent progress of self‐assembling NIR‐absorbing endogenic pigments in fabricating nanomaterials toward biomedical applications. Functional nanomaterials based on bile pigments and melanins are mainly discussed with the emphasis on the design rules, nanostructures, and applications.