Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

A Novel Strategy to Introduce 18F, a Positron Emitting Radionuclide, into a Gallium Nitrate Complex: Synthesis, NMR, X-Ray Crystal Structure, and Preliminary Studies on Radiolabelling with 18F

Taracad K. Venkatachalam A C , Paul V. Bernhardt B , Damion H. R. Stimson A , Gregory K. Pierens A , Rajiv Bhalla A and David C. Reutens A
+ Author Affiliations
- Author Affiliations

A Center for Advanced Imaging, The University of Queensland, Brisbane, Qld 4072, Australia.

B School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, Australia.

C Corresponding author. Email: t.venkatachalam@uq.edu.au

Australian Journal of Chemistry - https://doi.org/10.1071/CH17334
Submitted: 16 June 2017  Accepted: 18 September 2017   Published online: 11 October 2017

Abstract

A hexan-3,4-dione bis(4N-phenylthiosemicarbazone) gallium nitrate complex was synthesised and the structure was confirmed by NMR studies. The complex was prepared using an appropriately substituted dithiosemicarbazone and sodium methoxide in anhydrous methanol. The structure was further confirmed using single crystal X-ray crystallography. The crystal structure of gallium nitrate complex of diphenylthiosemicarbazone comprise a planar configuration of the tetradentate coordinated thiosemicarbazone with the Ga3+ ion, with the nitrate ligand occupying the apical coordination site. The X-ray structure of the gallium fluoride complex of pentan-2,3-dione bis(4N-phenylthiosemicarbazone) has been determined and confirms exchange of the nitrate can be achieved with fluoride. We show facile exchange of 18F, a positron emitter, to form the 18F-gallium complex under mild conditions, thus providing confirmation that such a transformation can be used to introduce 18F directly into nitrate-coordinated complexes of gallium-thiosemicarbozone complexes, a new labelling strategy for the preparation of imaging agents.


References

[1]  R. Brockman, R. W. Sidwell, G. Arnett, S. Shaddix, Exp. Biol. Med. 1970, 133, 609.
         | CrossRef | 1:CAS:528:DyaE3cXktleltr4%3D&md5=c424b2346b03613e780897ec1c2700b9CAS |

[2]  R. W. Brockman, J. R. Thomson, M. J. Bell, H. E. Skipper, Cancer Res. 1956, 16, 167.
         | 1:STN:280:DyaG28%2FksF2ntw%3D%3D&md5=0230c9b240125d4089cb7cdb2d85541aCAS |

[3]  M. J. Campbell, Coord. Chem. Rev. 1975, 15, 279.
         | CrossRef | 1:CAS:528:DyaE2MXksFantL0%3D&md5=4993b22657b1f13836e30ded5239c931CAS |

[4]  T. S. Lobana, R. Sharma, G. Bawa, S. Khanna, Coord. Chem. Rev. 2009, 253, 977.
         | CrossRef | 1:CAS:528:DC%2BD1MXivVWisb8%3D&md5=0b04b96597cccc8a358b11b15c48cc1bCAS |

[5]  S. R. Turk, C. Shipman, J. C. Drach, J. Gen. Virol. 1986, 67, 1625.
         | CrossRef | 1:CAS:528:DyaL28Xls1Cntbg%3D&md5=84858123d9dee48d1a6a5f9a2be0ea27CAS |

[6]  D. X. West, A. E. Liberta, S. B. Padhye, R. C. Chikate, P. B. Sonawane, A. S. Kumbhar, R. G. Yerande, Coord. Chem. Rev. 1993, 123, 49.
         | CrossRef | 1:CAS:528:DyaK3sXhtlynsbo%3D&md5=598b9a5101680b5e0981cbe2e2dbe1ebCAS |

[7]  F. A. Beckford, A. Brock, A. Gonzalez-Sarrías, N. P. Seeram, J. Mol. Struct. 2016, 1121, 156.
         | CrossRef | 1:CAS:528:DC%2BC28XptVWitLw%3D&md5=0ddd7ddb93941e8fd6a57ff0b2ff2f7dCAS |

[8]  L. R. Bernstein, Pharmacol. Rev. 1998, 50, 665.
         | 1:CAS:528:DyaK1MXltFyhtg%3D%3D&md5=475aab3852a37bd970a5117203f41744CAS |

[9]  P. Collery, B. Keppler, C. Madoulet, B. Desoize, Crit. Rev. Oncol. Hematol. 2002, 42, 283.
         | CrossRef |

[10]  J. G. da Silva, L. S. Azzolini, S. M. Wardell, J. L. Wardell, H. Beraldo, Polyhedron 2009, 28, 2301.
         | CrossRef | 1:CAS:528:DC%2BD1MXnt1ajt7k%3D&md5=9c49e578775b25d1e002025406964b7eCAS |

[11]  D. Gambino, M. Fernandez, D. Santos, G. A. Etcheverria, O. E. Piro, F. R. Pavan, C. Q. Leite, I. Tomaz, F. Marques, Polyhedron 2011, 30, 1360.
         | CrossRef | 1:CAS:528:DC%2BC3MXksFSru7c%3D&md5=36e7b9b0163624eb7bb4fb1d10913d30CAS |

[12]  D. E. Green, C. L. Ferreira, R. V. Stick, B. O. Patrick, M. J. Adam, C. Orvig, Bioconjug. Chem. 2005, 16, 1597.
         | CrossRef | 1:CAS:528:DC%2BD2MXhtVGqs7vF&md5=205e5c11a859b94327d8d94e54a33fb6CAS |

[13]  S. E. Harpstrite, A. A. Beatty, S. D. Collins, A. Oksman, D. E. Goldberg, V. Sharma, Inorg. Chem. 2003, 42, 2294.
         | CrossRef | 1:CAS:528:DC%2BD3sXhsFGgur8%3D&md5=4836d26d38a0c99b1eb39788e86e4675CAS |

[14]  C. R. Kowol, R. Berger, R. Eichinger, A. Roller, M. A. Jakupec, P. P. Schmidt, V. B. Arion, B. K. Keppler, J. Med. Chem. 2007, 50, 1254.
         | CrossRef | 1:CAS:528:DC%2BD2sXhvFags7g%3D&md5=654054aa17430924360d99100b42773aCAS |

[15]  I. C. Mendes, M. A. Soares, R. G. dos Santos, C. Pinheiro, H. Beraldo, Eur. J. Med. Chem. 2009, 44, 1870.
         | CrossRef | 1:CAS:528:DC%2BD1MXjsl2htbc%3D&md5=adb2fd6418a161eac25468ffe176b33dCAS |

[16]  B. W. Tsang, C. J. Mathias, P. E. Fanwick, M. A. Green, J. Med. Chem. 1994, 37, 4400.
         | CrossRef | 1:CAS:528:DyaK2MXhvFahsLw%3D&md5=6358f7502088eb2bb1903b49616ffca6CAS |

[17]  S. I. Pascu, P. A. Waghorn, T. D. Conry, B. Lin, H. M. Betts, J. R. Dilworth, R. B. Sim, G. C. Churchill, F. I. Aigbirhio, J. E. Warren, Dalton Trans. 2008, 2107.
         | CrossRef | 1:CAS:528:DC%2BD1cXkvFGhur0%3D&md5=7c3ce13c5c5582cfaebe92452ff39664CAS |

[18]  S. I. Pascu, P. A. Waghorn, B. W. Kennedy, R. L. Arrowsmith, S. R. Bayly, J. R. Dilworth, M. Christlieb, R. M. Tyrrell, J. Zhong, R. M. Kowalczyk, Chem. Asian J. 2010, 5, 506.
         | CrossRef | 1:CAS:528:DC%2BC3cXktVSmtrg%3D&md5=a65f54f80a6dfa991c5a86bbb5adb8faCAS |

[19]  R. Bhalla, C. Darby, W. Levason, S. K. Luthra, G. McRobbie, G. Reid, G. Sanderson, W. Zhang, Chem. Sci. 2014, 5, 381.
         | CrossRef | 1:CAS:528:DC%2BC3sXhvVGntLzE&md5=bf98f17f104249dc922a728ca9ae54eeCAS |

[20]  R. Bhalla, W. Levason, S. K. Luthra, G. McRobbie, G. Sanderson, G. Reid, Chem. – Eur. J. 2015, 21, 4688.
         | CrossRef | 1:CAS:528:DC%2BC2MXktVeqsrc%3D&md5=2c6d4b4ee81c4e800954024e1311f86cCAS |

[21]  T. Venkatachalam, G. Pierens, P. V. Bernhardt, D. Stimson, R. Bhalla, L. Lambert, D. Reutens, Aust. J. Chem. 2016, 69, 1033.
         | CrossRef | 1:CAS:528:DC%2BC28XhsVOitrjP&md5=d4f99299ec66dfa9b693190f838a1989CAS |

[22]  G. M. Sheldrick, Acta Cryst. Sect. A 2008, 64, 112.
         | 1:CAS:528:DC%2BD2sXhsVGhurzO&md5=933d4ded754510f3d6dd59e45c48aab3CAS |

[23]  L. J. Farrugia, J. Appl. Cryst. 1999, 32, 837.
         | CrossRef | 1:CAS:528:DyaK1MXlsVSlurk%3D&md5=e0ff15107f5b5db7053aa30bb6753041CAS |

[24]  L. J. Farrugia, J. Appl. Cryst. 2012, 45, 849.
         | CrossRef | 1:CAS:528:DC%2BC38XhtVKltbzK&md5=4b3d869e655994706c63c7c42cc72f36CAS |

[25]  J. Chan, A. L. Thompson, M. W. Jones, J. M. Peach, Inorg. Chim. Acta 2010, 363, 1140.
         | CrossRef | 1:CAS:528:DC%2BC3cXjs1Wqu7w%3D&md5=1f14f7a141463df6279a80d1b613096cCAS |

[26]  G. L. Parrilha, K. S. Ferraz, J. A. Lessa, K. N. de Oliveira, B. L. Rodrigues, J. P. Ramos, E. M. Souza-Fagundes, I. Ott, H. Beraldo, Eur. J. Med. Chem. 2014, 84, 537.
         | CrossRef | 1:CAS:528:DC%2BC2cXht1GrsL3I&md5=7934a41f4aa47d26bb556e06ac0bf19eCAS |

[27]  N. Zhang, Y. Tai, M. Li, P. Ma, J. Zhao, J. Niu, Dalton Trans. 2014, 43, 5182.
         | CrossRef | 1:CAS:528:DC%2BC2cXjslGnsbs%3D&md5=4225b7d2000faf6f74f0713cb119b08eCAS |

[28]  I. S. Alam, R. L. Arrowsmith, F. Cortezon-Tamarit, F. Twyman, G. Kociok-Köhn, S. W. Botchway, J. R. Dilworth, L. Carroll, E. O. Aboagye, S. I. Pascu, Dalton Trans. 2016, 45, 3650.
         | CrossRef | 1:CAS:528:DC%2BC28XitFGisbY%3D&md5=113a68425c71a140cfcff0e78939922dCAS |

[29]  R. L. Arrowsmith, P. A. Waghorn, M. W. Jones, A. Bauman, S. K. Brayshaw, Z. Hu, G. Kociok-Köhn, T. L. Mindt, R. M. Tyrrell, S. W. Botchway, Dalton Trans. 2011, 40, 6238.
         | CrossRef | 1:CAS:528:DC%2BC3MXmvF2qurs%3D&md5=c764505c5f414487d2e4f5d3d9d946abCAS |



Supplementary MaterialSupplementary Material (913 KB) Export Citation