Synthesis of water-soluble camptothecin-polyoxetane conjugates via click chemistry

Mol Pharm. 2012 Nov 5;9(11):3403-8. doi: 10.1021/mp3005066. Epub 2012 Oct 23.

Abstract

Water-soluble camptothecin (CPT)-polyoxetane conjugates were synthesized using a clickable polymeric platform P(EAMO) that was made by polymerization of acetylene-functionalized 3-ethyl-3-(hydroxymethyl)oxetane (i.e., EAMO). CPT was first modified with a linker 6-azidohexanoic acid via an ester linkage to yield CPT-azide. CPT-azide was then click coupled to P(EAMO) in dichloromethane using bromotris(triphenylphosphine)copper(I)/N,N-diisopropylethylamine. For water solubility and cytocompatibility improvement, methoxypolyethylene glycol azide (mPEG-azide) was synthesized from mPEG 750 g mol(-1) and click grafted using copper(II) sulfate and sodium ascorbate to P(EAMO)-g-CPT. (1)H NMR spectroscopy confirmed synthesis of all intermediates and the final product P(EAMO)-g-CPT/PEG. CPT was found to retain its therapeutically active lactone form. The resulting P(EAMO)-g-CPT/PEG conjugates were water-soluble and produced dose-dependent cytotoxicity to human glioma cells and increased γ-H2AX foci formation, indicating extensive cell cycle-dependent DNA damage. Altogether, we have synthesized CPT-polymer conjugates able to induce controlled toxicity to human cancer cells.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Antineoplastic Agents, Phytogenic / chemistry*
  • Antineoplastic Agents, Phytogenic / metabolism
  • Brain Neoplasms / drug therapy
  • Brain Neoplasms / pathology*
  • Camptothecin / chemistry*
  • Camptothecin / metabolism
  • Cell Survival / drug effects
  • Click Chemistry*
  • Glioma / drug therapy
  • Glioma / pathology*
  • Humans
  • Luciferases / metabolism
  • Molecular Structure
  • Polyethylene Glycols / chemistry
  • Polyethylene Glycols / metabolism
  • Polymers / chemical synthesis*
  • Polymers / chemistry
  • Polymers / metabolism
  • Propylene Glycols / chemistry*
  • Propylene Glycols / metabolism
  • Solubility
  • Tumor Cells, Cultured
  • Water / chemistry

Substances

  • Antineoplastic Agents, Phytogenic
  • Polymers
  • Propylene Glycols
  • poly(oxetane)
  • Water
  • Polyethylene Glycols
  • Luciferases
  • Camptothecin