Nuclear Medicine and Biology
Volume 37, Issue 3 , Pages 255-264 , April 2010

Preparation and biological evaluation of cyclopentadienyl-based 99mTc-complexes [(Cp-R)99mTc(CO)3] mimicking benzamides for malignant melanoma targeting

  • Harmel W. Peindy N'Dongo

      Affiliations

    • Institute of Inorganic Chemistry, University of Zürich, 190, CH-8057 Zurich, Switzerland
  • ,
  • Paula D. Raposinho

      Affiliations

    • Unidade de Ciências Químicas e Radiofarmacêuticas, Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2686-953 Sacavém, Portugal
  • ,
  • Célia Fernandes

      Affiliations

    • Unidade de Ciências Químicas e Radiofarmacêuticas, Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2686-953 Sacavém, Portugal
  • ,
  • Isabel Santos

      Affiliations

    • Unidade de Ciências Químicas e Radiofarmacêuticas, Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2686-953 Sacavém, Portugal
  • ,
  • Daniel Can

      Affiliations

    • Institute of Inorganic Chemistry, University of Zürich, 190, CH-8057 Zurich, Switzerland
  • ,
  • Paul Schmutz

      Affiliations

    • Institute of Inorganic Chemistry, University of Zürich, 190, CH-8057 Zurich, Switzerland
  • ,
  • Bernhard Spingler

      Affiliations

    • Institute of Inorganic Chemistry, University of Zürich, 190, CH-8057 Zurich, Switzerland
  • ,
  • Roger Alberto

      Affiliations

    • Institute of Inorganic Chemistry, University of Zürich, 190, CH-8057 Zurich, Switzerland
    • Corresponding Author InformationCorresponding author.

Received 26 October 2009 ,Revised 11 November 2009 ,Accepted 25 November 2009.

References 

  1. Camacho LH, Antonia S, Sosman J, Kirkwood JM, Gajewski TF, Redman B, et al. Phase I/II trial of tremelimumab in patients with metastatic melanoma. J Clin Oncol. 2009;27:1075–1081
  2. Buraggi GL, Callegaro L, Mariani G, Turrin A, Cascinelli N, Attili A, et al. Imaging with 131I-labeled monoclonal antibodies to a high-molecular-weight melanoma-associated antigen in patients with melanoma: efficacy of whole immunoglobulin and its F(ab′)2 fragments. Cancer Res. 1985;45:3378–3387
  3. Larson SM. Biologic characterization of melanoma tumors by antigen-specific targeting of radiolabeled anti-tumor antibodies. J Nucl Med. 1991;32:287–291
  4. Larsson B, Olander K, Dencker L, Holmqvist L. Accumulation of 125I-labelled thiouracil and propylthiouracil in murine melanotic melanomas. Br J Cancer. 1982;46:538–550
  5. Van Langevelde A, Bakker CN, Broxterman HJ, Journee-De Korver JG, Kaspersen FM, Oosterhuis JA, et al. Potential radiopharmaceuticals for the detection of ocular melanoma: Part I. 5-Iodo-2-thiouracil derivatives. Eur J Nucl Med. 1983;8:45–51
  6. Kloss G, Leven M. Accumulation of radioiodinated tyrosine derivatives in the adrenal medulla and in melanomas. Eur J Nucl Med. 1979;4:179–186
  7. Bubeck B, Eisenhut M, Heimke U, Zum Winkel K. Melanoma affine radiopharmaceuticals: I. A comparative study of 131I-labeled quinoline and tyrosine derivatives. Eur J Nucl Med. 1981;6:227–233
  8. Michelot JM, Moreau MF, Labarre PG, Madelmont JC, Veyre AJ, Papon JM, et al. Synthesis and evaluation of new iodine-125 radiopharmaceuticals as potential tracers for malignant melanoma. J Nucl Med. 1991;32:1573
  9. Michelot JM, Moreau MF, Veyre AJ, Bonafous JF, Bacin FJ, Madelmont JC, et al. Phase II scintigraphic clinical trial of malignant melanoma and metastases with iodine-123-N-(2-diethylaminoethyl 4-iodobenzamide). J Nucl Med. 1993;34:1260–1266
  10. John CS, Gulden ME, Li J, Bowen WD, Mcafee JG, Thakur ML. Synthesis, in vitro binding, and tissue distribution of radioiodinated 2-[125I]N-(N-benzylpiperidin-4-yl)-2-iodo benzamide, 2-[125I]BP: a potential sigma receptor marker for human prostate tumors. Nucl Med Biol. 1998;25:189–194
  11. Chehade F, De Labriolle-Vaylet C, Moins N, Moreau MF, Papon J, Labarre P, et al. Secondary ion mass spectrometry as a tool for investigating radiopharmaceutical distribution at the cellular level: the example of I-BZA and (14)C-I-BZA. J Nucl Med. 2005;46:1701–1706
  12. Guerquin-Kern JL, Hillion F, Madelmont JC, Labarre P, Papon J, Croisy A. Ultra-structural cell distribution of the melanoma marker iodobenzamide: improved potentiality of SIMS imaging in life sciences. Biomed Eng Online. 2004;3:10
  13. Cachin F, Chezal JM, Miot-Noirault E, Moins N, Auzeloux P, Vidal A, et al. Nouveaux traceurs TEMP: exemple des traceurs des protéoglycanes et de la mélanine. Médecine Nucléaire. 2009;33:161–167
  14. John CS, Vilner BJ, Bowen WD. Synthesis and characterization of [125I]-N-(N-benzylpiperidin-4-yl)-4- iodobenzamide, a new sigma receptor radiopharmaceutical: high-affinity binding to MCF-7 breast tumor cells. J Med Chem. 1994;37:1737–1739
  15. John CS, Bowen WD, Saga T, Kinuya S, Vilner BJ, Baumgold J, et al. A malignant melanoma imaging agent: synthesis, characterization, in vitro binding and biodistribution of iodine-125-(2-piperidinylaminoethyl)4-iodobenzamide. J Nucl Med. 1993;34:2169–2175
  16. Guo Z, Sadler PJ. Metals in medicine. Angew Chem Int Ed. 1999;38:1512–1531
  17. Schwochau K. Technetium radiopharmaceuticals — fundamentals, synthesis, structure, and development. Angew Chem Int Ed. 1994;33:2258–2267
  18. Dilworth JR, Suzanne JP. The biomedical chemistry of technetium and rhenium. Chem Soc Rev. 1998;27:43–55
  19. Bowen ML, Orvig C. 99m-Technetium carbohydrate conjugates as potential agents in molecular imaging. Chem Commun (Camb). 2008;5077–5091
  20. Bartholoma M, Valliant J, Maresca KP, Babich J, Zubieta J. Single amino acid chelates (SAAC): a strategy for the design of technetium and rhenium radiopharmaceuticals. Chem Commun (Camb). 2009;493–512
  21. Miao Y, Benwell K, Quinn TP. 99mTc- and 111In-labeled alpha-melanocyte-stimulating hormone peptides as imaging probes for primary and pulmonary metastatic melanoma detection. J Nucl Med. 2007;48:73–80
  22. Raposinho PD, Correia JDG, Alves S, Botelho MF, Santos AC, Santos I. A 99mTc(CO)3-labeled pyrazolyl-[alpha]-melanocyte-stimulating hormone analog conjugate for melanoma targeting. Nucl Med Biol. 2008;35:91–99
  23. Chen J, Cheng Z, Hoffman TJ, Jurisson SS, Quinn TP. Melanoma-targeting properties of (99m)technetium-labeled cyclic alpha-melanocyte-stimulating hormone peptide analogues. Cancer Res. 2000;60:5649–5658
  24. Auzeloux P, Papon J, Azim EM, Borel M, Pasqualini R, Veyre A, et al. A potential melanoma tracer: synthesis, radiolabeling, and biodistribution in mice of a new nitridotechnetium bis(aminothiol) derivative pharmacomodulated by a N-(diethylaminoethyl)benzamide. J Med Chem. 2000;43:190–198
  25. Eisenhut M, Mohammed A, Mier W, Schonsiegel F, Friebe M, Mahmood A, et al. Melanoma uptake of (99m)Tc complexes containing the N-(2-diethylaminoethyl)benzamide structural element. J Med Chem. 2002;45:5802–5805
  26. Friebe M, Mahmood A, Bolzati C, Drews A, Johannsen B, Eisenhut M, et al. [99mTc]Oxotechnetium(V) complexes amine-amide-dithiol chelates with dialkylaminoalkyl substituents as potential diagnostic probes for malignant melanoma. J Med Chem. 2001;44:3132–3140
  27. Top S, El Hafa H, Vessieres A, Quivy J, Vaissermann J, Hughes DW, et al. Rhenium carbonyl complexes of beta-estradiol derivatives with high affinity for the estradiol receptor: an approach to selective organometallic radiopharmaceuticals. J Am Chem Soc. 1995;117:8372–8380
  28. Salmain M, Gunn M, Gorfti A, Top S, Jaouen G. Labeling of proteins by organometallic complexes of rhenium: I. Synthesis and biological activity of the conjugates. Bioconjugate Chem. 1993;4:425–433
  29. Spradau TW, Katzenellenbogen JA. Preparation of cyclopentadienyltricarbonylrhenium complexes using a double ligand-transfer reaction. Organometallics. 1998;17:2009–2017
  30. Minutolo F, Katzenellenbogen JA. Boronic acids in the three-component synthesis of carbon-substituted cyclopentadienyl tricarbonyl rhenium complexes. J Am Chem Soc. 1998;120:13264–13265
  31. Masi S, Top S, Boubekeur L, Jaouen G, Mundwiler S, Spingler B, et al. Direct synthesis of tricarbonyl(cyclopentadienyl)rhenium and tricarbonyl(cyclopentadienyl)technetium units from ferrocenyl moieties — preparation of 17alpha-ethynylestradiol derivatives bearing a tricarbonyl(cyclopentadienyl)technetium group. Eur J Inorg Chem. 2004;2013–2017
  32. Wald J, Alberto R, Ortner K, Candreia L. Aqueous one-pot synthesis of derivatized cyclopentadienyl-tricarbonyl complexes of 99mTc with an in situ CO source: application to a serotonergic receptor ligand. Angew Chem Int Ed Engl. 2001;40:3062–3066
  33. Bernard J, Ortner K, Spingler B, Pietzsch HJ, Alberto R. Aqueous synthesis of derivatized cyclopentadienyl complexes of technetium and rhenium directed toward radiopharmaceutical application. Inorg Chem. 2003;42:1014–1022
  34. Liu Y, Spingler B, Schmutz P, Alberto R. Metal-mediated retro Diels–Alder of dicyclopentadiene derivatives: a convenient synthesis of [(Cp-R)M(CO)3] (M=99mTc, Re) complexes. J Am Chem Soc. 2008;130:1554–1555
  35. Peindy N'dongo HW, Liu Y, Can D, Schmutz P, Spingler B, Alberto R. Aqueous syntheses of [(Cp-R)M(CO)3] type complexes (Cp=cyclopentadienyl, M=Mn, 99mTc, Re) with bioactive functionalities. J Organomet Chem. 2009;694:981–987
  36. Top S, Lehn JS, Morel P, Jaouen G. Synthesis of cyclopentadienyltricarbonylrhenium(I) carboxylic acid from perrhenate. J Organomet Chem. 1999;583:63–68
  37. Peindy N'Dongo HW, Neundorf I, Merz K, Schatzschneider U. Synthesis, characterization, X-ray crystallography, and cytotoxicity of a cymantrene keto carboxylic acid for IR labelling of bioactive peptides on a solid support. J Inorg Biochem. 2008;102:2114–2119
  38. John CS, Vilner BJ, Gulden ME, Efange SM, Langason RB, Moody TW, et al. Synthesis and pharmacological characterization of 4-[125I]-N-(N-benzylpiperidin-4-yl)-4-iodobenzamide: a high affinity sigma receptor ligand for potential imaging of breast cancer. Cancer Res. 1995;55:3022–3027
  39. Mansard S, Papon J, Moreau MF, Miot-Noirault E, Labarre P, Bayle M, et al. Uptake in melanoma cells of N-(2-diethylaminoethyl)-2-iodobenzamide (BZA2), an imaging agent for melanoma staging: relation to pigmentation. Nucl Med Biol. 2005;32:451–458
  40. Labarre P, Papon J, Moreau MF, Moins N, Bayle M, Veyre A, et al. Melanin affinity of N-(2-diethylaminoethyl)-4-iodobenzamide, an effective melanoma imaging agent. Melanoma Res. 2002;12:115–121
  41. Pham TQ, Greguric I, Liu X, Berghofer P, Ballantyne P, Chapman J, et al. Synthesis and evaluation of novel radioiodinated benzamides for malignant melanoma. J Med Chem. 2007;50:3561–3572
  42. Moins N, D'Incan M, Bonafous J, Bacin F, Labarre P, Moreau MF, et al. 123I-N-(2-diethylaminoethyl)-2-iodobenzamide: a potential imaging agent for cutaneous melanoma staging. Eur J Nucl Med Mol I. 2002;29:1478–1484
  43. Xcalibur CCD system vers.. 171.32. Oxford, UK: Oxford Diffraction Ltd.; 2007;
  44. Altomare A, Burla MC, Camalli M, Cascarano GL, Giacovazzo C, Guagliardi A, et al. SIR97: a new tool for crystal structure determination and refinement. J. Appl. Cryst. 1999;32:115–119
  45. Sheldrick GM. A short history of SHELX. Acta Cryst. 2008;A64:112–122
  46. Spek AL. Single-crystal structure validation with the program PLATON. J. Appl. Cryst. 2003;36:7–13
  47. Alberto R, Ortner K, Wheatley N, Schibli R, Schubiger AP. Synthesis and properties of boranocarbonate: a convenient in situ CO source for the aqueous preparation of [99mTc(OH2)3(CO)3]+. J Am Chem Soc. 2001;123:3135–3136

 This work was supported by the Swiss Federal Secretariat for Research and Education under Contract No. SBF C06.0109 and by the University of Zurich.

PII: S0969-8051(09)00286-8

doi: 10.1016/j.nucmedbio.2009.11.006

Nuclear Medicine and Biology
Volume 37, Issue 3 , Pages 255-264 , April 2010