UV-cleavable unimolecular micelles: Synthesis and characterization toward photocontrolled drug release carriers

Xiao Liu, Zhicheng Tian, Chen Chen, Harry R. Allcock

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

UV-cleavable star polymers composed of a well-defined 6-arm amphiphilic block copolymer and a UV-cleavable core with photolabile o-nitrobenzyl groups have been synthesized and characterized. The core of the star polymer is a cyclotriphosphazene, which can biodegrade to phosphate and ammonium ion. The resultant unimolecular micelles can be dissociated in a controlled manner by UV irradiation. The inner lipophilic poly(methyl methacrylate) (PMMA) and the outer hydrophilic poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMA) were grafted by atom transfer radical polymerization (ATRP), leading to the formation of star-PMMA-PPEGMA with different compositions. The effects of various factors, such as molecular weight, solution concentration, solvents (THF, toluene, and water) and monomers (MMA, PEGMA, and 2-(dimethylamino)ethyl methacrylate (DMA)) on the photodegradation rate of the star polymers were studied by gel permeation chromatography (GPC). The micellar behavior of star-PMMA-PPEGMA was unambiguously demonstrated by dynamic light scattering (DLS), fluorescence techniques and transmission electron microscopy (TEM). The formation of nanoparticles (star-AGG) from the aggregation of the two star-PMMA-PPEGMA polymer micelles in aqueous solution was detected by DLS with hydrodynamic radii of 86 and 111 nm. The critical aggregation concentration (CAC) of star-AGG-2 from star-PMMA179-PPEGMA89-2 was 0.0026 g L-1 and 0.022 g L-1 before and after UV-irradiation indicating the reduced stability of the polymer micellar structures after UV-irradiation due to the detachment of the amphiphilic arms from the cyclotriphosphazene core. As a result, spontaneous dissociation of cleaved micelles can be induced by the dilution effect in the human body for stimulus-controlled drug release.

Original languageEnglish (US)
Pages (from-to)1115-1125
Number of pages11
JournalPolymer Chemistry
Volume4
Issue number4
DOIs
StatePublished - Feb 21 2013

Fingerprint

Drug Carriers
Micelles
Stars
Polymethyl Methacrylate
Polymers
Pharmaceutical Preparations
Polymethyl methacrylates
Methyl Ethers
Irradiation
Dynamic light scattering
Ethylene Glycol
Methacrylates
Photolysis
Toluene
Hydrodynamics
Transmission Electron Microscopy
Human Body
Polymerization
Nanoparticles
Gel Chromatography

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Biochemistry
  • Biomedical Engineering
  • Polymers and Plastics
  • Organic Chemistry

Cite this

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title = "UV-cleavable unimolecular micelles: Synthesis and characterization toward photocontrolled drug release carriers",
abstract = "UV-cleavable star polymers composed of a well-defined 6-arm amphiphilic block copolymer and a UV-cleavable core with photolabile o-nitrobenzyl groups have been synthesized and characterized. The core of the star polymer is a cyclotriphosphazene, which can biodegrade to phosphate and ammonium ion. The resultant unimolecular micelles can be dissociated in a controlled manner by UV irradiation. The inner lipophilic poly(methyl methacrylate) (PMMA) and the outer hydrophilic poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMA) were grafted by atom transfer radical polymerization (ATRP), leading to the formation of star-PMMA-PPEGMA with different compositions. The effects of various factors, such as molecular weight, solution concentration, solvents (THF, toluene, and water) and monomers (MMA, PEGMA, and 2-(dimethylamino)ethyl methacrylate (DMA)) on the photodegradation rate of the star polymers were studied by gel permeation chromatography (GPC). The micellar behavior of star-PMMA-PPEGMA was unambiguously demonstrated by dynamic light scattering (DLS), fluorescence techniques and transmission electron microscopy (TEM). The formation of nanoparticles (star-AGG) from the aggregation of the two star-PMMA-PPEGMA polymer micelles in aqueous solution was detected by DLS with hydrodynamic radii of 86 and 111 nm. The critical aggregation concentration (CAC) of star-AGG-2 from star-PMMA179-PPEGMA89-2 was 0.0026 g L-1 and 0.022 g L-1 before and after UV-irradiation indicating the reduced stability of the polymer micellar structures after UV-irradiation due to the detachment of the amphiphilic arms from the cyclotriphosphazene core. As a result, spontaneous dissociation of cleaved micelles can be induced by the dilution effect in the human body for stimulus-controlled drug release.",
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UV-cleavable unimolecular micelles : Synthesis and characterization toward photocontrolled drug release carriers. / Liu, Xiao; Tian, Zhicheng; Chen, Chen; Allcock, Harry R.

In: Polymer Chemistry, Vol. 4, No. 4, 21.02.2013, p. 1115-1125.

Research output: Contribution to journalArticle

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AB - UV-cleavable star polymers composed of a well-defined 6-arm amphiphilic block copolymer and a UV-cleavable core with photolabile o-nitrobenzyl groups have been synthesized and characterized. The core of the star polymer is a cyclotriphosphazene, which can biodegrade to phosphate and ammonium ion. The resultant unimolecular micelles can be dissociated in a controlled manner by UV irradiation. The inner lipophilic poly(methyl methacrylate) (PMMA) and the outer hydrophilic poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMA) were grafted by atom transfer radical polymerization (ATRP), leading to the formation of star-PMMA-PPEGMA with different compositions. The effects of various factors, such as molecular weight, solution concentration, solvents (THF, toluene, and water) and monomers (MMA, PEGMA, and 2-(dimethylamino)ethyl methacrylate (DMA)) on the photodegradation rate of the star polymers were studied by gel permeation chromatography (GPC). The micellar behavior of star-PMMA-PPEGMA was unambiguously demonstrated by dynamic light scattering (DLS), fluorescence techniques and transmission electron microscopy (TEM). The formation of nanoparticles (star-AGG) from the aggregation of the two star-PMMA-PPEGMA polymer micelles in aqueous solution was detected by DLS with hydrodynamic radii of 86 and 111 nm. The critical aggregation concentration (CAC) of star-AGG-2 from star-PMMA179-PPEGMA89-2 was 0.0026 g L-1 and 0.022 g L-1 before and after UV-irradiation indicating the reduced stability of the polymer micellar structures after UV-irradiation due to the detachment of the amphiphilic arms from the cyclotriphosphazene core. As a result, spontaneous dissociation of cleaved micelles can be induced by the dilution effect in the human body for stimulus-controlled drug release.

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