Au@p4VP core@shell pH-sensitive nanocomposites suitable for drug entrapment

  • J Colloid Interface Sci. 2018 Mar 15:514:704-714. doi: 10.1016/j.jcis.2017.12.072.
Joaquim Clara-Rahola  1 Ana Moscoso  2 Ana Belén Ruiz-Muelle  3 Marco Laurenti  4 Petr Formanek  5 Juan M Lopez-Romero  2 Ignacio Fernández  3 J Fernando Diaz  6 Jorge Rubio-Retama  4 Andreas Fery  7 Rafael Contreras-Cáceres  8
Affiliations
  • 1. I2TiC Multidisciplinary Research Group, Open University of Catalonia, 08035 Barcelona, Spain; Eikhonal Research, 08750 Barcelona, Spain. Electronic address: [email protected].
  • 2. Department of Organic Chemistry, Faculty of Sciences, University of Malaga, 29071 Málaga, Spain.
  • 3. Department of Chemistry and Physics, Research Centre CIAIMBITAL, University of Almería, Ctra. Sacramento, s/n, 04120 Almería, Spain.
  • 4. Department of Physical-Chemistry II, Pharmacy Faculty, Complutense University of Madrid, Spain.
  • 5. Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, 01069 Dresden, Germany.
  • 6. Department of Chemical and Physical Biology, Centro de Investigaciones Biológicas, Consejo Superior de Investigaciones Científicas, Ramiro de Maeztu 9, 28040 Madrid, Spain.
  • 7. Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, 01069 Dresden, Germany; Physical Chemistry of Polymeric Materials, Technische Universität Dresden, 01069 Dresden, Germany; Cluster of Excellence Centre for Advancing Electronics Dresden (cfaed), Germany.
  • 8. Department of Organic Chemistry, Faculty of Sciences, University of Malaga, 29071 Málaga, Spain; Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, 01069 Dresden, Germany.
Abstract

We synthesize and characterize pH-responsive hybrid nanocomposites with SERS and drug loading applications. This colloidal system is structured by spherical 50 nm Au cores individually coated by a pH-sensitive shell of poly4-vinylpyridine (Au@p4VP). The synthesis of these hybrid nanocomposites is performed in two steps, a first one involves the fabrication of vinyl-functionalized Au nanoparticles, and a second one includes the controlled overgrowth of a p4VP shell by free radical polymerization. As a result, Au@p4VP hybrid systems with a mean diameter ranging from 150 to 57 nm are obtained upon varying the monomer concentration at synthesis. Au@p4VP nanocomposite exhibits pH-response capabilities, confirmed by cryo-TEM analysis, Small Angle X-ray Scattering (SAXS) and Zeta Potential (ZP) measurements at different pH conditions. The Au@p4VP particles also display a controllable swelling response, which depends on the cross-linker density within the polymer. This swelling capability is analyzed by Dynamic Light Scattering (DLS), and UV-vis spectroscopy at different pHs. The pH-responsive capability is here exploited for the chemical entrapment of doxorubicin hydrochloride (Dox) into the polymer network. The presence of this molecule is resolved by Surface Enhanced Raman Spectroscopy (SERS) measurements. The entrapment efficiency of Dox by the Au@p4VP system is determined via NMR spectroscopy of the supernatants.

Keywords
Cryo-TEM; Gold nanoparticles; Nanocomposite system; SERS; Stimuli-responsive.
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