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WIREs Nanomed Nanobiotechnol
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Recent advances on small‐molecule nanomedicines for cancer treatment

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Abstract Nanomedicines have made important contributions in the development of cancer therapies due to their tumor selectivity, multifunctionality, and synergistic effect between the payloads. In addition to the required pharmaceutical ingredients, nanomedicines are generally composed of nonpharmaceutical excipients. These excipients generally form a large proportion of the nanomedicine, and they may have potential toxicity and greatly increase the cost for drug development. Small molecule nanomedicines (SMNs) minimize or abandon the excipients and are directly assembled from pharmaceutical ingredients, which can largely improve the drug delivery efficiency and biosafety while also relieving the financial burden of drug development. In this review, we summarize recently developed SMNs that are composed of a single drug, physical mixtures of multiple drugs, drug–drug covalent conjugates, dyes with drugs, photosensitizers with drugs, photosensitizers with peptides, and drugs with peptides. This review focuses on the SMN's applications in cancer treatments, their limitations, and the future development outlook of SMNs. We hope that our insights on SMNs may be helpful to the future of drug development and make nanomedicine more powerful in the battle with cancer. This article is categorized under: Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease
Schematic illustration of small‐molecule nanomedicines (SMNs), their composition, and their functionalities. The merits of SMNs include: (a) High DL%: The SMNs that directly assembled by drugs can reach a 100% drug loading. (b) Green: The SMNs that co‐assembled or self‐assembled by physically mixing of drugs involve no chemical synthetic steps. (c) Bioavailability: The SMNs can extensively increase the water solubility of hydrophobic drugs, thus improving the bioavailability. (d) Controllability: By introducing some functional building blocks, such as peptides, the morphology, drug release, and DL% of SMNs can be highly controllable; (e) Multifunctionality: Some building blocks, such as photosensitizers, peptides, and dyes, offer the SMNs with multiple functionalities. (f) Synergy: The synergistic effect between different drugs gives better efficacy on cancer treatments. (g) Diagnosis: Imaging agents, such as dye and contrast agents, render SMNs with excellent diagnostic capability. Abbreviations: DL, drug loading; PS: photosensitizer
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Photosensitizer‐peptide SMNs. (a) Self‐assembly of photosensitizer‐peptide composed SMNs and the functionalities of their building blocks. (b) Self‐assembly of photosensitizer and small peptide (FF) conjugates. Reprinted with permission from Zou et al. () American Chemical Society. (c) Self‐assembly of a photosensitizer (Ce6) and amino acid (Fmoc‐L‐L) coordinated complex. Reprinted with permission from H. Zhang et al. () American Chemical Society. (d) Self‐assembly of photosensitizer (Ce6) and amino acid (Fmoc‐H) coordinated complex. Reprinted with permission from S. Li et al. () American Chemical Society. (e) Co‐assembly of photosensitizer and peptide (Fmoc‐L3‐OMe) doped SMNs. Reprinted with permission from J. Li et al. () American Chemical Society
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Highly controllable SMN assembled by drug–peptide conjugates. (a) Schematic illustration of the molecular assembly and PTX‐promoted supramolecular polymerization of Spax. Reprinted with permission from Su, Zhang, Wang, Wang, and Cui () American Chemical Society. (b) Composition and self‐assembly of three different drug–peptide SMNs, dCPT‐Sup35, CPT‐Cap‐Sup35, and dCapSup35 SMNs. Reprinted with permission from Ma et al. () Elsevier B.V. (c) The chemical structures of dual‐drug and peptide conjugates and their corresponding nanostructure of the self‐assemblies (dCPT‐Sup35, CPT‐PTX‐Sup35, and dPTX‐Sup35). Reprinted with permission from Cheetham, Zhang, et al. () Royal Society of Chemistry. (d) Schematic illustration of the compositions and the self‐assembly process of the drug–peptide amphiphiles. The drug (CPT) and β‐sheet‐forming peptide were conjugated together through reducible disulfide bond with adjustable CPT ratios. Reprinted with permission from Cheetham et al. () American Chemical Society. (e) The chemical structures and morphology of two drug–peptide‐based SMNs that are able to control the drug release due to the linker between the drug and peptide. These two SMNs were composed of an ester‐based CPT‐buSS‐Tau (1) and a carbonate‐based CPT‐etcSS‐Tau (2), respectively. Reprinted with permission from Cheetham, Ou, et al. () Royal Society of Chemistry
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Drug–peptide SMNs with multifunctionality. (a) Self‐assembly of drug–peptide SMNs and the functionalities of the individual building blocks. (b) Molecular structure and self‐assembly behavior of drug–peptide conjugate (CPT‐LFPR) SMNs and their morphological transformation based on an autocatalytic growth mechanism. Reprinted with permission from D.‐B. Cheng et al. () American Chemical Society. (c) Self‐assembly of the curcumin–amino acid coordinated complex. Reprinted with permission from Y. Li et al. () Wiley‐VCH
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Photosensitizer–drug SMNs. (a) Co‐assembly of chlorin e6‐HCPT‐doped SMNs. Reprinted with permission from Wen et al. () Royal Society of Chemistry. (b) Self‐assembly of H2TPyP‐Curcumin‐perylene co‐doped SMNs. Reprinted with permission from J. Zhang, Liang, et al. () American Chemical Society. (c) Self‐assembly of ursolic acid–paclitaxel–ICG co‐doped SMNs. Reprinted with permission from Guo et al. () American Chemical Society. (d) Co‐assembly of EPI‐DOX doped SMNs. Reprinted with permission from Yang Li et al. () Elsevier B.V. (e) Co‐assembly of DOX‐ICG‐doped SMNs. Reprinted with permission from N. Zhang et al. () Elsevier B.V
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Drug–drug conjugate SMNs. (a) Self‐assembly and the advantages of drug–drug conjugate SMNs. (b) Self‐assembly of GT–CPT SMNs. Reprinted with permission from M. Hou et al. () Royal Society of Chemistry. (c) Synthesis and self‐assembly of amphiphilic prodrug CPT‐ss‐Ir into SMNs. Reprinted with permission from He et al. () Royal Society of Chemistry. (d) Self‐assembly of FdU–BdM twin drug nanoparticles. Reprinted with permission from T. Zhang et al. () American Chemical Society. (e) Synthesis and self‐assembly of the amphiphilic drug–drug conjugate (ADDC) into SMNs. Reprinted with permission from Huang et al. () American Chemical Society
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Photosensitizer–drug‐based SMNs with size and charge transformability. Self‐assembly of pPhD NPs and their therapeutic and diagnostic functionalities. Reprinted with permission from Xue, Huang, Bo, et al. () Nature Publishing Group
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Self‐assembly of photosensitizer–drug SMNs. (a) Schematic illustration of the self‐assembly and functionalities of photosensitizer–drug‐based SMNs. (b) Schematic illustration of FAPIN and its therapeutic and diagnostic functionalities. Reprinted with permission from Xue, Huang, Wang, et al. () Elsevier B.V
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Drug–dye SMNs. (a) Self‐assembly of drug–dye‐based SMN; (b) self‐assembly of TPE‐DOX‐doped SMN (TD NPs) and their subcellular behaviors. Reprinted with permission from Xue et al. () Wiley‐VCH. (c) Self‐assembly of TPE‐DOX conjugates‐based SMN (THyD NPs) and their “from darkness to brightness” cellular imaging property. Reprinted with permission from Xue et al. () American Chemical Society
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Multidrug doped SMNs. (a) Self‐assembly of multidrug doped SMNs and their advantages. (b) Self‐assembly of HCPT and DOX co‐assembled SMNs (HD NPs) and their morphology. Reprinted with permission from F. Chen et al. () American Chemical Society. (c) Co‐assembly of CST/DOX NPs. Reprinted with permission from Y. Xiao et al. () Royal Society of Chemistry. (d) Co‐assembly of MDNCs and their compositions. Reprinted with permission from Zhou et al. () Elsevier B.V. (e) Co‐assembly of ternary cocktail NPs. Reprinted with permission from Huang et al. () American Chemical Society
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Single drug‐composed SMNs. (a) Self‐assembly of single drug SMN. Schematic illustration of (b) UA NPs and FITC‐UA NPs. Reprinted with permission from Fan et al. () American Chemical Society. (c) Functionalized self‐carried Cur NPs from nanoparticle formation and PEGylation to delivery. Reprinted with permission from J. Zhang, Li, et al. () Royal Society of Chemistry. (d) Preparation and functionalization of HCPT NPs. Reprinted with permission from W. Li et al. () Royal Society of Chemistry
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