Stimuli-Responsive Drug-Delivery Systems Based on Supramolecular Nanovalves  Zheng Li, Nan Song, Ying-Wei Yang  Matter  Volume 1, Issue 2, Pages 345-368 (August 2019) DOI: 10.1016/j.matt.2019.05.019 Copyright © 2019 Elsevier Inc. Terms and Conditions

Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 1 Chemical Structures Chemical structures of some typical stalk components used in the construction of supramolecular nanovalves. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 2 Schematic Representation of Drug-Delivery Systems Incorporated with Supramolecular Nanovalves for Controllable Drug Delivery The systems covered in this review are based on inorganic nanoparticles (NPs), metal-organic frameworks (MOFs), and supramolecular assemblies. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 3 Schematic Representation of Supramolecular Nanovalves Installed on the Surface of Mesoporous Silica Nanoparticles (A) Illustrations of cyclodextrin-based supramolecular nanovalves triggered by near-infrared (NIR) light. Reproduced with permission from Han et al.60 Copyright 2018, American Chemical Society. (B) CuS NPs modified by cyclodextrin as gatekeepers for the controlled release of doxorubicin (DOX) drug. Reproduced with permission from Li et al.62 Copyright 2017, American Chemical Society. (C) Monoferrocene-functionalized cyclodextrin as gated materials for redox-triggered release of DOX. Reproduced with permission from Wang et al.34 Copyright 2015, American Chemical Society. (D) Illustration of phosphonated pillar[5]arene (PPA[5])-based supramolecular nanovalve. Reproduced with permission from Huang et al.64 Copyright 2017, American Chemical Society. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 4 Schematic Illustration of the Preparation of Magnetic Supramolecular Nanovalves for Multistimuli-Responsive Cargo Release BDA, 1,4-butanediamine; HMSN, hollow mesoporous silica nanoparticles; GA3, gibberellic acid. Reproduced with permission from Li et al.65 Copyright 2019, Royal Society of Chemistry. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 5 Schematic Illustration of the Chemo-Photothermal Nanotheranostic System Constructed from UiO-66 MOF as Drug Carrier and Pillar[6]arene Pseudorotaxanes as Supramolecular Nanovalves (A) The preparation of PUWPFa NPs scaffolds by installing pillarene nanovalves onto polypyrrole@UiO-6 nanohybrids via a layer-by-layer assembly strategy. (B) Cytotoxicity assay and cell viability with the treatment of PUWPFa NPs toward human hepatocyte cells (L02) and human cervical cancer cells (HeLa cells). (C) Photographs of the xenograft female mice with HeLa tumor in the treatment of phosphate-buffered saline (PBS) control, 5-fluorouracil (5-Fu), PUWPFa NPs + NIR laser, and 5-Fu-loaded PUWPFa NPs + NIR laser, respectively. (D) Release profiles of 5-Fu upon different temperatures and periodic irradiation (2 W/cm2) of 808-nm NIR laser. Reproduced with permission from Wu et al.67 Copyright 2018, American Chemical Society. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 6 Schematic Illustration of Supramolecular Assembled Pt-PAZMB-b-POEGMA Nanoplatform (A) The chemical structure and synthetic route of Pt-PAZMB-b-POEGMA. (B) GSH-responsive disassembly of the supramolecular assembled nanostructures for the release of therapeutic agents. Reproduced with permission from Yu et al.68 Copyright 2017, American Chemical Society. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 7 Schematic Illustration of Supramolecular Assembled Theranostic NPs The host-guest complexation of β-cyclodextrin and CPT on CD-SS-CPT promoted the formation of supramolecular polymer-based NPs, and the endogenous GSH induced the disassociation of the supramolecular theranostic NPs to release camptothecin (CPT) for cancer therapy. Reproduced with permission from Yu et al.69 Copyright 2018, American Chemical Society. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 8 Schematic Illustration of a Carboxylatopillar[6]arene-Based Supramolecular Vesicle Formation of supramolecular vesicles via the self-assembly of a carboxylatopillar[6]arene, suitable guest molecules, and model drugs for quintuple stimuli-responsive cargo release, and the chemical structures of the key components involved in these processes. HAD, hexanediamine. Reproduced with permission from Jiang et al.70 Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 9 Schematic Illustration of the DOX-Loaded Supramolecular Polymer Vehicles Based on Cyclodextrins for Controlled Release The coassembly of PAA-CD, PAA-SS-AD, PEG-AD, and DOX to result in DOX-loaded supramolecular NPs for dual-stimuli-responsive release of DOX. Reproduced with permission from Ang et al.73 Copyright 2016, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 10 Schematic Representation of the Metal-Organic Polyhedron for Controlled Release (A) Synthetic route to the monofunctionalized cucurbituril host and the chemical structures of host and guests. (B) pH-chemical and pH-photochemical responsive release processes. Reproduced with permission from Samanta et al.75 Copyright 2017, American Chemical Society. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 11 Schematic Description of Drug-Loaded Nanohybrids Based on Core-Shell Upconversion NPs for Controlled Release The schematic preparation of drug-loaded nanohybrids based on nanostructured core-shell upconversion NPs (UCNPs) gated by water-soluble pillar[5]arene (WP5)-based host-guest complexes, chemical structures of the individual components, and the related biomedical application. UCL, upconversion luminescence; MRI, magnetic resonance imaging. Reproduced with permission from Li et al.78 Copyright 2018, American Chemical Society. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 12 Schematic Description of Supramolecular Nanosystem Based on Phosphoryl Pillar[5]arenes-Coated β-NaYF4:Yb/Er UCNPs for Targeted Drug Delivery and Upconversion Luminescence Cell Imaging Phosphoryl pillar[5]arenes (PP5) were decorated on the outside of OA-UCNPs through ligand-exchange process for further drug delivery and controlled release. Reproduced with permission from Yang et al.76 Copyright 2018, Royal Society of Chemistry. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 13 Schematic Description of Supramolecular Switch for Antimicrobial Regulations Supramolecular assembly and disassembly process for the regulation of antimicrobial activity. PPV, poly(-phenylene vinylene); AD, adamantane; CB[7], cucurbit[7]uril. Reproduced with permission from Bai et al.85 Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 14 Schematic Description of Layer-by-Layer Self-Assembled Multihybrid Materials for Antimicrobial Application (A) The construction of MSN-Lys-HA-PGMA multihybrid antimicrobial nanomaterial and its antimicrobial mechanism. Reproduced with permission from Wu et al.86 Copyright 2015, American Chemical Society. (B) Representation of multihybrid nanoassembly based on MSN, synthetic macrocycle, and AIEgen, and its on-off switchable antimicrobial mechanism. Reproduced with permission from Li et al.87 Copyright 2017, American Chemical Society. Matter 2019 1, 345-368DOI: (10.1016/j.matt.2019.05.019) Copyright © 2019 Elsevier Inc. Terms and Conditions