Synthesis of Aza-BODIPY Boron Difluoride PDT Agents to Promote Apoptosis in HeLa Cells

Priefer, Ronny; Griffiths, Justin R.; Ludwig, Janelle N.; Skelhorne‐Gross, Graham; Greene, Robert S.

doi:10.2174/157017811796064377

Cited by 9 publications

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“…Owing to their advantageous and tunable photophysical properties and ability to generate singlet oxygen ( 1 O 2 )c oupled with absorption of light from the socalled "therapeuticw indow"( 600 nm-1100 nm), aza-BODIPY dyes have been proposed as potential triplet photosensitizers for both anti-microbiala nd anti-cancer photodynamic therapy. [20,[30][31][32][33][34][35][36][37][38][39][40][41] Aza-BODIPYs continue to attracta ttention as chemosensors for the detection of ammonia, [42] cysteine, homocysteine and glutathione in living cells, [43] Hg 2 + , [44][45][46] F À , [47,48] in vivo detection of H 2 S, [49] carbon dioxide, [50] glucosei nw hole blood, [51] detection of saxitoxin [52] and pH-sensitive sensors. [52] Furthermore, aza-BODIPYs have been proposed as photoactive components in photovoltaic devices [54][55][56] and nonlinear optical materials.…”

Section: Introductionmentioning

confidence: 99%

“…The consequence of the introduction of an aza‐bridge into the structure of the BODIPY chromophore system is the bathochromic shift of both absorption and emission bands of around 80 nm. Owing to their advantageous and tunable photophysical properties and ability to generate singlet oxygen ( 1 O 2 ) coupled with absorption of light from the so‐called “therapeutic window” (600 nm–1100 nm), aza‐BODIPY dyes have been proposed as potential triplet photosensitizers for both anti ‐microbial and anti ‐cancer photodynamic therapy . Aza‐BODIPYs continue to attract attention as chemosensors for the detection of ammonia, cysteine, homocysteine and glutathione in living cells, Hg 2+ , F − , in vivo detection of H 2 S, carbon dioxide, glucose in whole blood, detection of saxitoxin and pH‐sensitive sensors .…”

Section: Introductionmentioning

confidence: 99%

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Visible‐Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis, Photophysics and Redox Properties

Gut

Łapok

Drelinkiewicz

et al. 2017

Chemistry An Asian Journal

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As eries of novel iodinated NO 2 -substituted azaBODIPYs have been synthesized and characterized.H ighly desirable photophysical and photochemical properties were induced in NO 2 -substituted aza-BODIPYs by iodinationo ft he pyrrole rings. In particular, highv alues of singlet oxygen quantum yields (F D )r anging from 0.79 to 0.85 were measured. The photooxygenation process proceeds via aT ype II mechanism under the experimental conditions applied. The compounds studied exhibited an absorption band within the so-called "therapeutic window", with l max located between 645 nm to 672 nm. They were non-fluorescent at room temperature with excited singlet-state lifetimes within the picosecond range as measured by femtosecond transient absorption. Nanosecond laser flash photolysis experiments revealed T 1 !T n absorption spanning from ca. 400 nm to ca. 500 nm and allowedd etermination of the triplet-state lifetimes. The estimated triplet lifetimes (t T )i nd eaerated acetonitrile ranged between 2.74 msa nd 3.50 ms. As estimated by CV/DPV measurements, all iodinateda za-BODIPYs studied exhibited one irreversible oxidation and two quasireversible reductions processes. Estimation of the E HOMO gave the value of À6.06 to À6.26 eV while the E LUMO was found to be located at ca. À4.6 eV.T hermogravimetric (TGA) analysis revealed that iodinated aza-BODIPYs weres table up to approximately 300 8C. All compounds studied exhibit high photostability in toluene solution.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Visible‐Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis, Photophysics and Redox Properties

Gut

Łapok

Drelinkiewicz

et al. 2017

Chemistry An Asian Journal

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“…Aza‐BODIPY‐a , aza‐BODIPY‐b , and rhodium(III) tetrakis‐4‐tolylporphyrin chloride ([Rh III (ttp)Cl]) were prepared according to literature procedures. The Rh III (ttp)‐aza‐BODIPY conjugates were linked either through the para position of the phenyl substituent of the aza‐BODIPY fluorophore ( 1 a ) or through one of the meta positions ( 1 b ).…”

Section: Resultsmentioning

confidence: 99%

Rational Design of Emissive NIR‐Absorbing Chromophores: Rh^III Porphyrin‐Aza‐BODIPY Conjugates with Orthogonal Metal–Carbon Bonds

Zhou

Gai

Zhou

et al. 2016

Chemistry A European J

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The facile synthesis of Group 9 Rh(III) porphyrin-aza-BODIPY conjugates that are linked through an orthogonal Rh-C(aryl) bond is reported. The conjugates combine the advantages of the near-IR (NIR) absorption and intense fluorescence of aza-BODIPY dyes with the long-lived triplet states of transition metal rhodium porphyrins. Only one emission peak centered at about 720 nm is observed, irrespective of the excitation wavelength, demonstrating that the conjugates act as unique molecules rather than as dyads. The generation of a locally excited (LE) state with intramolecular charge-transfer (ICT) character has been demonstrated by solvatochromic effects in the photophysical properties, singlet oxygen quantum yields in polar solvents, and by the results of density functional theory (DFT) calculations. In nonpolar solvents, the Rh(III) conjugates exhibit strong aza-BODIPY-centered fluorescence at around 720 nm (ΦF =17-34 %), and negligible singlet oxygen generation. In polar solvents, enhancements of the singlet-oxygen quantum yield (ΦΔ =19-27 %, λex =690 nm) have been observed. Nanosecond pulsed time-resolved absorption spectroscopy confirms that relatively long-lived triplet excited states are formed. The synthetic methodology outlined herein provides a useful strategy for the assembly of functional materials that are highly desirable for a wide range of applications in material science and biomedical fields.

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“…Replacement of the meso‐carbon atom with an aza‐bridge results in a bathochromic shift of both absorption ( λ abs ) and emission ( λ fl ) bands of around 80 nm. Owing to their advantageous photophysical properties (triplet lifetimes τ T , triplet state quantum yields Φ T and triplet state energies E T ) combined with tunable singlet oxygen quantum yields (Φ Δ ) and ability to absorb light from the “therapeutic window”, aza‐BODIPYs have been proposed as potential triplet photosensitizers for both anti ‐microbial and anti ‐cancer photodynamic therapy . Furthermore, aza‐BODIPYs were considered as fluorescent chemosensors for the detection of ammonia, cysteine, homocysteine and glutathione in living cells, Hg 2+ , F − , in vivo detection of H 2 S and NO, carbon dioxide, glucose in whole blood and pH‐sensitive sensors .…”

Section: Introductionmentioning

confidence: 99%

Near‐Infrared Photoactive Aza‐BODIPY: Thermally Robust and Photostable Photosensitizer and Efficient Electron Donor

et al. 2020

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We report herein the synthesis of aza-BODIPY substituted with strongly electron-donating p-(diphenylamino)phenyl substituents (p-Ph 2 NÀ ) at 3,5-positions. The presence of p-Ph 2 NÀ groups lowers the energy of the singlet excited state (E s ) to 1.48 eV and induces NIR absorption with λ abs at 789 nm in THF. The compound studied is weakly emissive with the emission band (λ f ) at 837 nm and with the singlet lifetime (τ S ) equal to 100 ps. Nanosecond laser photolysis experiments of the aza-BODIPY in question revealed T 1 !T n absorption spanning from ca. 350-550 nm with the triplet lifetime (τ T ) equal to 21 μs. By introducing a heavy atom (Br) into the structure of the aza-BODIPY, we managed to turn it into a NIR operating photosensitizer. The photosensitized oxygenation of the model compound-diphenylisobenzofuran (DPBF)-proceedes via Type I and/or Type III mechanism without formation of singlet oxygen ( 1 O 2 ). As estimated by CV/DPV measurements, the p-Ph 2 NÀ substituted aza-BODIPYs studied exhibits oxidation processes at relatively low oxidation potentials (E ox 1 ), pointing to the very good electron-donating properties of these molecules. Extremely high photostability and thermal robustness up to approximately 300°C are observed for the p-Ph 2 NÀ substituted aza-BODIPYs. [a] Dr. . Synthesis of mono-bromo aza-BODIPY 7. Reaction conditions: a) acetyl chloride, ZnCl 2 , DCM, 0°C to reflux, 24 h, 45 %; b) 4-tert-butylbenzaldehyde, NaOH, EtOH, 0°C to RT, 24 h, 69 %; c) MeNO 2 , K 2 CO 3 , MeOH, reflux, 17 h, 79 % ; d) CH 3 COONH 4 ,n-butanol, 117°C, 3 h, 63 %; e) BF 3 · Et 2 O, DIPA, DCM, 1 h, 91 %; f) NBS, DCM, 2 h, 0°C, 96 %.ChemPhysChem Articles

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Synthesis of Aza-BODIPY Boron Difluoride PDT Agents to Promote Apoptosis in HeLa Cells

Cited by 9 publications

References 0 publications

Visible‐Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis, Photophysics and Redox Properties

Visible‐Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis, Photophysics and Redox Properties

Rational Design of Emissive NIR‐Absorbing Chromophores: Rh^III Porphyrin‐Aza‐BODIPY Conjugates with Orthogonal Metal–Carbon Bonds

Near‐Infrared Photoactive Aza‐BODIPY: Thermally Robust and Photostable Photosensitizer and Efficient Electron Donor

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Synthesis of Aza-BODIPY Boron Difluoride PDT Agents to Promote Apoptosis in HeLa Cells

Cited by 9 publications

References 0 publications

Visible‐Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis, Photophysics and Redox Properties

Visible‐Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis, Photophysics and Redox Properties

Rational Design of Emissive NIR‐Absorbing Chromophores: RhIII Porphyrin‐Aza‐BODIPY Conjugates with Orthogonal Metal–Carbon Bonds

Near‐Infrared Photoactive Aza‐BODIPY: Thermally Robust and Photostable Photosensitizer and Efficient Electron Donor

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Rational Design of Emissive NIR‐Absorbing Chromophores: Rh^III Porphyrin‐Aza‐BODIPY Conjugates with Orthogonal Metal–Carbon Bonds