Highly Fluorous Porphyrins as Model Compounds for Molecule Interferometry

Tüxen, Jens; Eibenberger, Sandra; Gerlich, Stefan; Arndt, Markus; Mayor, Marcel

doi:10.1002/ejoc.201100638

Cited by 25 publications

(25 citation statements)

References 34 publications

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“…The p -fluoro phenyl group of porphyrin 1 underwent nucleophilic substitution with the primary amino group of Boc-protected polyamines 42 and commercially available tert -butyl-12-amino-4,7,10-trioxadodecanoate, 43,44 as shown in Scheme 1. Deprotection of the Boc and tert -butyl protecting groups using TFA in dichloromethane, gave conjugates 2 – 9 in 91% overall yields, after reversed-phase HPLC purification.…”

Section: Resultsmentioning

confidence: 99%

“…All Boc-protected polyamines were synthesized as previously described. 42 1-Mercaptomethyl- p -carborane was prepared from p -carborane, as described in literature. 45 …”

Section: Methodsmentioning

confidence: 99%

“…To porphyrin 1 (14.9 mg, 0.01 mmol) were added (N1,N3,N6–tri- tert -butoxycarbonyl)-1,8-di-amino-3,6-diazaoctane 42 (6.7 mg, 0.015 mmol) and NMP (2 mL) 43,44 and the mixture was heated at 100 °C for 4 h. After cooling to room temperature, the solution was diluted with ethyl acetate (50 mL) and washed with brine (5 x 50 mL). The organic layer was dried over anhydrous sodium sulfate, the solvents removed under vacuum and the resulting reddish brown residue purified by silica gel column chromatography using dichloromethane for elution, followed by dichloromethane/ethyl acetate 9:1.…”

Section: Methodsmentioning

confidence: 99%

“…A similar procedure was used to that described above for conjugate 2 , using porphyrin 1 (14.9 mg, 0.01 mmol), (N1,N3,N6,N9,N12-penta-tert-butoxycarbonyl)-1,14-di-amino-3,6,9,12-tetraazatetradecane 42 (11.0 mg, 0.015 mmol) and NMP (2 mL). 43,44 The Boc-protected conjugate was obtained (21.4 mg) in 96% yield, mp = 293–296 0 C; UV-vis (DMSO) λ max (ε/M −1 cm −1 ) 416 (456 000), 510 (24 000), 555 (21 000), 585 (12 500), 650 (10 300).…”

Section: Methodsmentioning

confidence: 99%

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Synthesis and cellular studies of polyamine conjugates of a mercaptomethyl–carboranylporphyrin

Bhupathiraju

Vicente

2013

Bioorganic & Medicinal Chemistry

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Seven polyamine conjugates of a tri(p-carboranylmethylthio)tetrafluorophenylporphyrin were prepared in high yields by sequential substitution of the p-phenyl fluoride of tetrakis(pentafluorophenyl)porphyrin (TPPF), and investigated as boron delivery agents for boron neutron capture therapy (BNCT). The polyamines used were derivatives of the natural-occurring spermine with different lengths of the carbon chains, terminal primary amine groups and, in two of the conjugates, additional aminoethyl moieties. A tri(polyethylene glycol) conjugate was also synthesized for comparison purposes. The polyamine conjugates showed low dark cytotoxicity (IC50 > 400 μM) and low phototoxicity (IC50 > 40 μM at 1.5 J/cm2). All polyamine conjugates, with one exception, showed higher uptake into human glioma T98G cells (up to 12-fold) than the PEG conjugate, and localized preferentially in the cell ER, Golgi and the lysosomes. Our results show that spermine derivatives can serve as effective carriers of boronated porphyrins for the BNCT of tumors.

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Section: Resultsmentioning

confidence: 99%

“…All Boc-protected polyamines were synthesized as previously described. 42 1-Mercaptomethyl- p -carborane was prepared from p -carborane, as described in literature. 45 …”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and cellular studies of polyamine conjugates of a mercaptomethyl–carboranylporphyrin

Bhupathiraju

Vicente

2013

Bioorganic & Medicinal Chemistry

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“…This problem can be overcome by perfluoroalkyl-functionalization of a stable organic core. This may reduce their polarizability and raise their volatility [16]. But even then, the sublimation and evaporation enthalpy increases with the molecular mass.…”

Section: Introductionmentioning

confidence: 99%

Single-Photon Ionization of Organic Molecules Beyond 10 kDa

Schmid

Stöhr

Arndt

et al. 2013

J. Am. Soc. Mass Spectrom.

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The volatilization and soft ionization of complex neutral macromolecules at low energies has remained an outstanding challenge for several decades [1]. Most volatilization techniques in mass spectrometry produce ions already in the source and most of them lead to particle velocities in excess of several hundred meters per second. For many macromolecules, post-ionization is inefficient since electronic or optical excitations can be followed by competing non-ionizing internal conversion, electron recapture, or fragmentation processes. Here, we explore the laser-assisted volatilization of neutral perfluoroalkyl-functionalized tetraphenylporphyrins as well as their single-photon ionization using vacuum ultraviolet (VUV) light at 157 nm. A systematic investigation of the ionization curves allows us to determine the molecular velocity distribution and ionization cross sections. We demonstrate the detection of single photon ionized intact organic molecules in excess of 10 kDa from a slow molecular beam.

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Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy

Gutsche

Ortwerth

Gräfe

et al. 2016

Chemistry A European J

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Abstract:The application of porphyrinoids in biomedical fields like photodynamic therapy (PDT) requires the introduction of functional groups to adjust their solubility in the biological environment and to allow a coupling to other active moieties or carrier systems. A valuable motif in this regard is the pentafluorophenyl (PFP)-substituent, as the PFP-group easily undergoes a regiospecific nucleophilic replacement (S N Ar) of the para-fluorine atom by a number of nucleophiles. Here, it is shown that -alternatively to an amino-substitution on the final porphyrinoid or BODIPY -the precursor 5-(PFP)-dipyrrane can be modified with amines (or alcohols). These dipyrranes were transformed into amino-substituted BODIPYs. Condensation of these dipyrranes with aldehydes gives access to trans-A 2 B 2 -porphyrins and -A 2 B-corroles. Using pentafluorobenzaldehyde another para-fluorine atom can be introduced enabling the synthesis of multifunctionalized tetrapyrroles. Furthermore, alkoxy-and amino-substituted dipyrranes were applied to the synthesis of A 3 B 3 -hexaphyrins. With this approach polar porphyrins can be prepared, which exhibit in vitro PDT activity against several tumor cell lines.

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Highly Fluorous Porphyrins as Model Compounds for Molecule Interferometry

Cited by 25 publications

References 34 publications

Synthesis and cellular studies of polyamine conjugates of a mercaptomethyl–carboranylporphyrin

Synthesis and cellular studies of polyamine conjugates of a mercaptomethyl–carboranylporphyrin

Single-Photon Ionization of Organic Molecules Beyond 10 kDa

Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy

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