Multipronged Biomimetic Approach To Create Optically Tunable Nanoparticles

Abstract

Current biomimetics for medical applications use as ingle biomimetic approach to imitate natural structures, which can be insufficient for reconstructing structurally complex natural systems.M ultipronged efforts may resolve these complexities.T oachieve interesting nanostructure-driven optical properties,adual-biomimetic system contained within asingle nanoagent was engineered to recapitulate chlorosomes, efficient light-harvesting organelles that have unique dye assemblies and tunable photonic properties.Aseries of chlorin dyes was synthesized, and these hydrophobic assemblies were stabilized inside ah igh-density lipoprotein, as econd biomimetic that enabled in vivo utility.This system resulted in tunable tumor imaging of intact (photoacoustic) and disrupted (activatable fluorescence) nanostructures.T he successful demonstration of this multipronged biomimetic approach opens the door for reconstruction of complex natural systems for biomedical applications.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Tailoring Porphyrin Conjugation for Nanoassembly-Driven Phototheranostic Properties

“…The core/shell architecture of native lipoproteins naturally allows for the incorporation of various porphyrin conjugates into different nanoparticle subunits (shell or core). Our group has explored porphyrin loading into a lipoprotein shell by introducing amphiphilicity to the porphyrin molecule through lipid conjugation 19,22 or into a lipoprotein core by enhancing porphyrin hydrophobicity through oleylamide 25 or bis(oleate) conjugation. 24 Synthetic HDL-like nanoparticles recapitulate the structure of native lipoproteins; therefore, porphyrin conjugates of varying hydrophobicity can be easily incorporated into their structure.…”

“…33 BChl-oleylamide was synthesized using a similar protocol as described for Pyro-oleylamide previously. 25 Briefly, 50 nmol of bacteriochlorophyll acid (prepared as described by Kozyrev and coauthors) 34 in anhydrous N,N-dimethylformamide (DMF, 5 mL) were added to N,N,N′,N′-tetramethyl-O-(1Hbenzotriazol-1-yl)uronium hexafluorophosphate, (HBTU, 2.1 mol equiv), oleylamine (1 mol equiv), and N,N-diisopropylethylamine (DIPEA, 3 v/v%). After stirring at room temperature under argon for 1 h, the reaction mixture was concentrated under reduced pressure.…”

“…24 Recently, Harmatys and coauthors synthesized a series of hydrophobic chlorin derivatives that were encapsulated into a biomimetic HDL core, wherein the spatial constraints created by an ApoA-1 mimetic peptide resulted in dye J-aggregation characterized by a strong bathochromic shift (654 to 715 nm), enabling photoacoustic imaging. 25 These examples indicate that the approach toward porphyrin inclusion into lipoproteins (for example, core versus shell) may influence the biophotonic properties of the associated nanostructures. Despite an abundance of literature describing porphyrin incorporation into lipoproteins using a variety of conjugation approaches, the specific effects of the conjugate structure on the nanoparticle's biophotonic and phototherapeutic properties remain unclear.…”

Interfacing DNA nanotechnology and biomimetic photonic complexes: advances and prospects in energy and biomedicine

“…Effective PA imaging predominantly depends on the dye aggregates showing quenched fluorescence emission. PA imaging agents are prepared via templating or encapsulating those densely stacked dye aggregates using the self-assembled lipid [ 66 ], lipoprotein [ 67 ], and polymer [ 68 ] nanocarriers, which can facilitate the lifetime of blood circulation and accumulation of the dye at the tumor site. Inspired by natural light-harvesting systems, Zheng et al developed a series of porphyrin dye aggregates assisted by lipid assemblies for photoacoustic applications [ 69 ].…”

Molecular photoacoustic imaging with ultra-small gold nanoparticles

“…Molecularly specific labeling of a single target with thousands of organic chromophores is challenging. However, recent studies have reported development of organic dyes and dye aggregates encapsulated either in micelles or liposomes that can facilitate delivery of a large quantity of chromophores for biomolecular labeling [9][10][11][12]; this is a very promising direction in molecular PAI that is still in early stages of development.…”