Carboranyl-porphyrazines and derivatives for boron neutron capture therapy: From synthesis to in vitro tests

Pietrangeli, Daniela; Rosa, Angela; Ristori, Sandra; Salvati, Anna; Altieri, S.; Ricciardi, Giampaolo

doi:10.1016/j.ccr.2013.03.035

Cited by 38 publications

(17 citation statements)

References 165 publications

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“…Yield: 90% (4.2 g, 13.1 mmol). 1 1-Methyl-2-(1-thiohex-6-yl)-1,2-closo-dodecaborane (4). To a solution of 3 (3.4 g, 10.6 mmol) in MeOH (120 mL) concentrated HCl (35%, 12 mL) was added.…”

Section: Synthetic Proceduresmentioning

confidence: 99%

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Water-soluble carboranyl-phthalocyanines for BNCT. Synthesis, characterization, and in vitro tests of the Zn(ii)-nido-carboranyl-hexylthiophthalocyanine

et al. 2015

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The zinc(II) complex of the octa-anionic 2,3,9,10,16,17,23,24-octakis-(7-methyl-7,8-dicarba-nido-undeca-boran-8-yl)hexyl-thio-6,13,20,27-phthalocyanine (nido-[ZnMCHESPc]Cs8, 7) has been obtained in the form of caesium salt through mild deboronation of the neutral precursor, the closo-[ZnMCHESPc] complex, 6, with CsF. 6 has been synthesized, in turn, by heating a finely ground mixture of the appropriate phthalonitrile and zinc(II) acetate at 180.0 °C. The complexes have been characterized by elemental analyses, FT-IR, UV-visible absorption and fluorescence emission spectroscopy, and their structures were assessed by (1)H, (13)C, (11)B, and two-dimensional homo- and hetero-correlated NMR spectroscopy experiments. 7 showed appreciable solubility in water solution, together with a marked tendency to aggregate. Aggregation of 7 in the hydrotropic medium resulted in significant fluorescence quenching. Instead, fluorescence quantum yields (Φ(F)) of 0.14 and 0.08, and singlet oxygen quantum yields (Φ(Δ)) of 0.63 and 0.24 were obtained for 6 and 7, respectively, in a DMF solution. In vitro boron neutron capture therapy (BNCT) experiments, employing boron imaging techniques as implemented in qualitative and quantitative neutron autoradiography methods, showed that 7 is capable of increasing the boron concentration of two selected cancerous cell lines, the DHD/K12/TRb of rat colon adenocarcinoma and UMR-106 of rat osteosarcoma, with the large-size Cs(+) counter-ions used to neutralize the negatively charged carborane polyhedra not presenting a significant obstacle to the process. Taken together, BNCT and photophysical measurement results indicated that 7 is potentially suitable for bimodal or multimodal anticancer therapy.

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“…Yield: 90% (4.2 g, 13.1 mmol). 1 1-Methyl-2-(1-thiohex-6-yl)-1,2-closo-dodecaborane (4). To a solution of 3 (3.4 g, 10.6 mmol) in MeOH (120 mL) concentrated HCl (35%, 12 mL) was added.…”

Section: Synthetic Proceduresmentioning

confidence: 99%

“…The product was purified by chromatography on silica-gel ( pentane/CH 2 Cl 2 , 7 : 3) to give a white solid. Yield: 95% (3.4 g, 10.6 mmol) 1. H NMR δ H (400 MHz, CDCl 3 , Me 4 Si) 2.75 (2H, t, J = 7 Hz, -CH 2 -S-), 2.22 (3H, s, C carb -CH 3 ), 2.05 (2H, m), 1.9 (3H, s, CH 3 -CvO), 1.45 (4H, m), 1.25 (4H, m), 2.9-1.5 (80H, br, B-H).…”

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confidence: 99%

Water-soluble carboranyl-phthalocyanines for BNCT. Synthesis, characterization, and in vitro tests of the Zn(ii)-nido-carboranyl-hexylthiophthalocyanine

et al. 2015

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“…Another important aspect in the characterization of photosensitizers for photodynamic therapy is the fluorescence quantum yield (Φ F ) and its quantum yield (Φ Δ ) of the generation of oxygen reactive species under visible light irradiation [20,21]. To assess this property, we used an indirect method with diphenylisobenzofuran (DPBF) as chemical quencher, comparing their rate of degradation promoted by each of the synthesized phthalocyanine derivatives and by unsubstituted zinc(II)phthalocyanine (ZnPc) under the same conditions [22,23,24].…”

Section: Resultsmentioning

confidence: 99%

Photochemical and Photophysical Properties of Phthalocyanines Modified with Optically Active Alcohols

et al. 2015

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Three phthalocyanine derivatives were synthesized and characterized: one modified with a racemic mixture of 1-(4-bromophenyl)ethanol and two other macrocycles modified with each one of the enantioenriched isomers (R)-1-(4-bromophenyl)ethanol and (S)-1-(4-bromophenyl)ethanol. The compounds were characterized by 1 H-NMR spectroscopy, mass spectrometry, UV-Vis absorption, and excitation and emission spectra. Additionally, partition coefficient values and the quantum yield of the generation of oxygen reactive species were determined. Interestingly, the phthalocyanine containing a (R)-1-(4-bromophenyl)ethoxy moiety showed higher quantum yield of reactive oxygen species generation than other compounds under the same conditions. In addition, the obtained fluorescence microscopy and cell viability results have shown that these phthalocyanines have different interactions with mammary MCF-7 cells. Therefore, our results indicate that the photochemical and biological properties of phthalocyanines with chiral ligands should be evaluated separately for each enantiomeric species.

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“…Carborane moieties may be easily transformed into their corresponding nido-form, conferring increased solubility in aqueous media to the resulting boronated porphyrin. Efforts towards the synthesis of boronated porphyrins have been reviewed by Pietrangeli et al [117] Although many boronated porphyrins have been prepared to date, only a few have reached the clinic, primarily because of the need for a better understanding of their mechanism of tissue-selectivity, retention and biochemical action [106]. Tested in rats bearing C6 cerebral gliomas, the tetrakis-carborane-carboxylate ester of 2,4-bis-(α,βdihydroxyethyl) deuterioporphyrin IX (BOPP, compound 23, Figure 5) at 48 hours after administration (100 mg/kg of body weight) exhibited tumour/normal brain ratios of 400:1 and tumour/blood ratios of 11:1 [118].…”

Section: Porphyrins and Phthalocyaninesmentioning

confidence: 99%

Towards carborane-functionalised structures for the treatment of brain cancer

Calabrese

Daou

Barbu

et al. 2018

Drug Discovery Today

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Boron neutron capture therapy (BNCT) is a promising targeted chemoradiotherapeutic technique for the management of invasive brain tumors, such as glioblastoma multiforme (GBM). A prerequisite for effective BNCT is the selective targeting of tumour cells with B-rich therapeutic moieties. To this end, polyhedral boranes, especially carboranes, have received considerable attention because they combine a high boron content with relative low toxicity and metabolic inertness. Here, we review progress in the molecular design of recently investigated carborane derivatives in light of the widely accepted performance requirements for effective BNCT.

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Carboranyl-porphyrazines and derivatives for boron neutron capture therapy: From synthesis to in vitro tests

Cited by 38 publications

References 165 publications

Water-soluble carboranyl-phthalocyanines for BNCT. Synthesis, characterization, and in vitro tests of the Zn(ii)-nido-carboranyl-hexylthiophthalocyanine

Water-soluble carboranyl-phthalocyanines for BNCT. Synthesis, characterization, and in vitro tests of the Zn(ii)-nido-carboranyl-hexylthiophthalocyanine

Photochemical and Photophysical Properties of Phthalocyanines Modified with Optically Active Alcohols

Towards carborane-functionalised structures for the treatment of brain cancer

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