The first example of an octadentate gadolinium unit based on DO3A (hydration number q=1) with a dithiocarbamate tether has been designed and attached to the surface of gold nanoparticles (around 4.4 nm in diameter). In addition to the superior robustness of this attachment, the restricted rotation of the Gd complex on the nanoparticle surface leads to a dramatic increase in relaxivity (r1) from 4.0 mm−1 s−1 in unbound form to 34.3 mm−1 s−1 (at 10 MHz, 37 °C) and 22±2 mm−1 s−1 (at 63.87 MHz, 25 °C) when immobilised on the surface. The one‐pot synthetic route provides a straightforward and versatile way of preparing a range of multifunctional gold nanoparticles. The incorporation of additional surface units for biocompatibility (PEG and thioglucose units) and targeting (folic acid) leads to little detrimental effect on the high relaxivity observed for these non‐toxic multifunctional materials. In addition to the passive targeting attributed to gold nanoparticles, the inclusion of a unit capable of targeting the folate receptors overexpressed by cancer cells, such as HeLa cells, illustrates the potential of these assemblies.
A robust dithiocarbamate tether allows novel gadolinium units based on DOTAGA (q=1) to be attached to the surface of gold nanoparticles (2.6–4.1 nm diameter) along with functional units offering biocompatibility, targeting and photodynamic therapy. A dramatic increase in relaxivity (r1) per Gd unit from 5.01 mm−1 s−1 in unbound form to 31.68 mm−1 s−1 (10 MHz, 37 °C) is observed when immobilised on the surface due to restricted rotation and enhanced rigidity of the Gd complex on the nanoparticle surface. The single‐step synthetic route provides a straightforward and versatile way of preparing multifunctional gold nanoparticles, including examples with conjugated zinc–tetraphenylporphyrin photosensitizers. The lack of toxicity of these materials (MTT assays) is transformed on irradiation of HeLa cells for 30 minutes (PDT), leading to 75 % cell death. In addition to passive targeting, the inclusion of units capable of actively targeting overexpressed folate receptors illustrates the potential of these assemblies as targeted theranostic agents.
Gold nanorods (GNRs) show great promise as photothermal therapy agents due to their remarkable ability to convert light into heat. In most cases, gold nanorods are synthesised via a seed-mediated method assisted by surfactants. However, the toxicity of these surfactants, principally cetrimonium ions, has prevented GNRs from being used more widely
in vivo
. To address this issue, various detoxification and functionalisation approaches have been proposed in recent years to replace or cover surfactant coatings on the gold surface. In this short review, the advantages and limitations of each approach are examined in the context of the recent progress made towards the design of GNRs suitable for use in the body.
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