Multimetallic Arrays: Bi-, Tri-, Tetra-, and Hexametallic Complexes Based on Gold(I) and Gold(III) and the Surface Functionalization of Gold Nanoparticles with Transition Metals

Knight, Edward R.; Leung, Nina H.; Thompson, Amber L.; Hogarth, Graeme; Wilton‐Ely, James D. E. T.

doi:10.1021/ic802442d

Cited by 47 publications

(22 citation statements)

References 70 publications

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“…When desired, the addition of K 2 CO 3 followed by carbon disulfide, leads to the in situ formation of the expected dithiocarbamate moiety (9), in line with our previous studies on piperazine-based dithiocarbamate complexes. [35,36,38,44,[49][50][51][52][53][54][55] High-resolution mass spectrometry confirmed the generation of 9 (m/z 812.1283f or [M+ +K] + ), while solid state infrared absorptions measured for 9 attributed to n(CN) and n(CS) at 1427 and 1002 cm À1 ,r espectively,p rovided evidencefor the formationofthe dithiocarbamate. This was reinforcedb yaresonance at 209.5 ppm in the 13 C{ 1 H} NMR spectrum obtained for the diamagneticl anthanum (La 3 + ,f 0 )a nalogue of 9,formed in an identical fashion.…”

Section: Synthesis Of Anovel Gadolinium Surface Unitmentioning

confidence: 90%

“…Our interest in the surface functionalisation of gold nanoparticles (GNPs) with metal complexes began in 2008, [34] and since then much of our work [33][34][35][36][37][38] has focused on the use of dithiocarbamate (R 2 NCS 2 À )t ethers as an alternative to the ubiquitous thiol(ate) or disulfide attachment methodologies for GNPs. Competition experiments [38,39] have demonstrated that dithiocarbamates are able to displace thiol(ate)s from the surface of the nanoparticle, but not vice versa. This more robust attachment methodology is gaining popularity but there are still relatively few examples of metals being tethered to GNPs in this way.…”

Section: Introductionmentioning

confidence: 99%

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Combined Magnetic Resonance Imaging and Photodynamic Therapy Using Polyfunctionalised Nanoparticles Bearing Robust Gadolinium Surface Units

Chabloz

Perry

Yoon

et al. 2020

Chemistry A European J

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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.

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Section: Synthesis Of Anovel Gadolinium Surface Unitmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Combined Magnetic Resonance Imaging and Photodynamic Therapy Using Polyfunctionalised Nanoparticles Bearing Robust Gadolinium Surface Units

Chabloz

Perry

Yoon

et al. 2020

Chemistry A European J

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“…An exciting new development in the area of golddithiocarbamate chemistry is the stabilization of gold nanoparticles by chelating dithiocarbamate ligands [92][93][94][95][96][97]. These are extremely easy to prepare, show good stability and allow decoration of the nanoparticles with a range of different functional groups.…”

Section: Tris(dithiocarbamate)mentioning

confidence: 99%

Metal-dithiocarbamate complexes: chemistry and biological activity

Hogarth¹

2012

MRMC

254

157

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Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors.

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“…Much of this work has focused on the use of dithiocarbamate (R 2 NCS 2 − ) tethers rather than the usual thiol(ate) or disulfide attachment methodologies. Competition experiments by us and others have shown that dithiocarbamates are able to displace thiol(ate)s from the surface of the nanoparticle, but not vice versa. Surprisingly, this robust attachment approach has still not been embraced widely with only relatively few examples of metals being tethered to GNPs in this way .…”

Section: Introductionmentioning

confidence: 99%

Polyfunctionalised Nanoparticles Bearing Robust Gadolinium Surface Units for High Relaxivity Performance in MRI

Chabloz

Wenzel

Perry

et al. 2019

Chemistry A European J

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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.

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Multimetallic Arrays: Bi-, Tri-, Tetra-, and Hexametallic Complexes Based on Gold(I) and Gold(III) and the Surface Functionalization of Gold Nanoparticles with Transition Metals

Cited by 47 publications

References 70 publications

Combined Magnetic Resonance Imaging and Photodynamic Therapy Using Polyfunctionalised Nanoparticles Bearing Robust Gadolinium Surface Units

Combined Magnetic Resonance Imaging and Photodynamic Therapy Using Polyfunctionalised Nanoparticles Bearing Robust Gadolinium Surface Units

Metal-dithiocarbamate complexes: chemistry and biological activity

Polyfunctionalised Nanoparticles Bearing Robust Gadolinium Surface Units for High Relaxivity Performance in MRI

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