Multifunctional Theranostic Platform Based On Water Soluble Perylene Diimide

Perylene-3,4,9,10-tetracarboxylic acid diimide derivatives have been extensively studied as industrial colorants,both as dyes(soluble)and pigments(insoluble),thanks to their high chemical,thermal,and photochemical stabilities,good optoelectronic property,easy modification,and extremely low cost.With development of science technology,perylene diimide was wildly utilized in various electronic and optical applications,such as organic field-effect transistors(OFETs),organic photovoltaic cells(OPVs)and orangic leaser,due to their excellent photophysical property and electronic properties.As a kind of semiconducting material,perylene diimide was also be developed to be some imaging agent applied in bioimaging and biosensor.With careful modification,perylene diimide with rigid aromatic ring plane and poor solubility could self-assembly in solvents to fabricate nano structures and improve its emission properties.Perylene diimide structure owned active area,imide position and bay position,which can be modified to improve its solubility in organic or aqueous solvent and photophysical property.In our design,we modified perylene diimide by its bay position with near infrared absorption,and polyethylene glycol act as water soluble part.Amphiphilic perylene diimide structure will be easily to realize the self assemblies.By tuning the ratio of organic solvent and water,we can prepare homogeneous nanoparticals with different size.Also,nanoparticles can be mulitifunctionlized by further surface modified,which applied into cancer cells mark,photoacoustic imaging,PET imaging and so on.With good photothermal ability,perylene diimide can be as a kind of photothermal agent to kill cancer cells.Simultaneously,the nano platform based on perylene diimide could become drug delivery system to realize the photoacoustic imaging guided therapy.The specific studies are as follows.1,Homogeneous near-infrared emissive polymeric nanoparticles based on amphiphilic diblock copolymers with perylene diimide and PEG pendants: self-assembly behavior and cellular imaging applicationIn this work,asymmetric PDI functionalized with acrylate moieties was synthesized and then the amphiphilic diblock copolymers PPDA-b-P(PEGMA)were obtained via RAFT polymerization.PNPs with NIR emission were conviniently obtained through the direct self-assembly of the as-synthesized amphiphilic diblock polymer in water.This self-assembly contributed to PPDA aggregation through hydrophobic interactions and therefore enhanced the efficient p–p stacking of PDI groups to produce NIR emission.Furthermore,the PEGMA-encapsulation of the PNPs provided them with good water solubility and low cytotoxicity,which made these PNPs good candidates for live cell imaging.Our study demonstrated a convenient method to fabricate NIR-emitting PNPs with good water solubility and biocompatibilty through the self-assembly of amphiphilic diblock copolymers2,Perylene-diimide-Based nanoparticles as highly efficient photoacoustic agents for deep brain tumor imaging in living miceIn this work,PDI NPs were successfully prepared and used to realize PAI of deep orthotopic brain tumor in mice models.Because of its low cost,ease of chemical modifications,and extraordinary high photostability,PDI system exhibits high potential for PAI of deep tumor.Furthermore,selecting contrast agents with appropriate light absorption capability and/or controlling their concentrations in tumor in an appropriate extent may be essential to obtain good PAI of deep tumor.Overall,our work provides insight on how to design or choose appropriate organic NP-based contrast agents for promoting the development of PAI technology for deep tumor imaging.3,Impact of semiconducting perylene diimide nanoparticle size on lymph node mapping and cancer imagingWe have successfully developed a series of PDI NPs with different sizes of 30,60,100,and 200 nm,exhibiting excellent PA and PTT effects and serving as a dual PET and PA imaging probe and photothermal agent.The precise size control over the PDI NPs can be achieved by tuning the concentration of the initial concentration of PDI molecules in the self-assembly process.Extremely low CAC value and PEG protection facilitated the excellent stability and biocompatibility.By taking full advantage of these multifunctional PDI NPs,PA and PET imaging study revealed size-dependent LN and tumor accumulation effect.It was demonstrated that 100 nm PDI NPs are most suitable for LN mapping and 60 nm PDI NPs are ideal for passive tumor targeting.Thus,our study not only presents organic semiconducting PDI NP theranostics but also proposes different sized NPs for multiple biomedical applications.4,Pillar[5]arene-perylene diimide based amphiphilic supramolecule: fabrication,controllable self-assembly and application in photoacoustic targeted drug deliveryIn this work,we designed pillar P5éPDI,a kind of supermolecular switch,in which pillar is host part and perylene diimide is guest part.Host pillar onwed nine triethylene glycol and one PEG2000 with biotin in the end,which provide water solubility and compatibility.Guest perylene diimide with a viologen group can react with pillar to form the supermolecular structure.This supermolecular structure can self assemble into water and form nanoparticles,due to strong hydrophobic properties of perylene diimide itself.Cooperated with long alkyl chain,perylene diimide based supermolecular system could be loading cancer drugs.With the EPR effect and active targeting ability,this supramolecular platform can be as theranostic platform to make photoacoustic imaging guided therapy for mice.