Recent Advances of the Near-infrared Fluorescent BODIPY/aza-BODIPY Dyes

doi:10.7517/issn.1674-0475.191216

Abstract

Abstract: This review covers the design, synthesis and functionalization of BODIPY/aza-BODIPY as fluorophore probes since 2002, including applications for fluorescence quenching, metal ion, anion, biomolecular detection, etc. Synthesis, properties and application of novel aza-BODIPY, substituted aza-BODIPY on the boron center, new near-Infrared-fluorescent aza-BODIPY dyes with 1-methyl-1H-pyrrolyl substituents at the 3, 5-positions and so forth, were herein discussed.

Key words: aza-BODIPY, near infrared fluorescent dye, singlet oxygen, chemical sensors, amino acid

YUE Shuai, SHAO Zhumei, JIANG Xindong. Recent Advances of the Near-infrared Fluorescent BODIPY/aza-BODIPY Dyes[J]. Imaging Science and Photochemistry, 2020, 38(4): 585-600.

References

[1] Ntziachristos V, Ripoll J, Weissleder R. Would near-infrared fluorescence signals propagate through large human organs for clinical studies?[J]. Optics Letters, 2002, 27(18):333-335.
[2] Becker A, Hessenius C, Licha K, et al. Receptor-targeted optical imaging of tumors with near-infrared fluorescent ligands[J]. Nature Biotechnology, 2001, 19(4):327-331.
[3] Descalzo A B, Rurack K. On the signalling pathways and Cu(Ⅱ)-mediated anion indication of N-meso-substituted heptamethine cyanine dyes[J]. Chemistry:A European Journal, 2009, 15(3):3173-3185.
[4] Barthram A M, Cleary R L, Kowallick R, et al. A new redoxtunable near-IR dye based on a trinuclear ruthenium(Ⅱ) complex of hexahydroxytriphenylene[J]. Chemical Communications, 1998, (24):2695-2696.
[5] Li H, Nguyen N, Fronczek F R, et al. Syntheses and properties of octa-, tetra-, and di-hydroxy-substituted phthalocyanines[J]. Tetrahedron, 2009, 65(17):3357-3363.
[6] Reents R, Wagner M, Kuhlmann J, et al. Synthesis and application of fluorescence-labeled Ras-proteins for live-cell imaging[J]. Angewandte Chemie International Edition, 2004, 43(20):2711-2714.
[7] Burghart A, Thoresen L H, Chen J, et al. Energy transfer cassettes based on BODIPY dyes[J]. Chemical Communications, 2000, 2203-2204.
[8] Beer G, Niederalt C, Grimme S, et al. Redox dwitches with chiroptical signal expression based on binaphthyl boron dipyrromethene conjugates[J]. Angewandte Chemie International Edition, 2000, 39:3252-3255.
[9] Umezawa K, Nakamura Y, Makino H, et al. Bright, color-tunable fluorescent dyes in the visible-near-infrared region[J]. Journal of the American Chemical Society, 2008, 130(5):1550-1551.
[10] Chen J, Reibenspies J, Derecskei-Kovacs A, et al. Through-space ¹³C-¹⁹F coupling can reveal conformations of modified BODIPY dyes[J]. Chemical Communications, 1999, (24):2501-2502.
[11] Descalzo A B, Xu H J, Xue Z L, et al. Phenanthrene-fused boron-dipyrromethenes as bright long-wavelength fluorophores[J]. Optics Letters, 2008, 10(8):1581-1584.
[12] Okujima T, Tomimori Y, Nakamura J, et al. Synthesis of π-expanded BODIPY and their fluorescent properties in the visible-near-infrared region[J]. Tetrahedron, 2010, 66:6895-6900.
[13] Kowada T, Yamaguchi S, Ohe K. Highly fluorescent BODIPY dyes modulated with spirofluorene moieties[J]. Optics Letters, 2010, 12(2):296-299.
[14] Boens N, Leen V, Dehaen W. Fluorescent indicators based on BODIPY[J]. Chemical Society Reviews, 2012, 41(3):1130-1172.
[15] Lu H, Mack J, Yang Y, et al. Structural modification strategies for the rational design of red/NIR region BODIPY[J]. Chemical Society Reviews, 2014, 43(13):4778-4823.
[16] Killoran J, Allen L, Gallagher J, et al. Synthesis of BF₂ chelates of tetraarylazadipyrromethenes and evidence for their photodynamic therapeutic behavior[J]. Chemical Communications, 2002, (17):1862-1863.
[17] Gorman A, Killoran J, O'Shea C, et al. In vitro demonstration of the heavy-atom effect for photodynamic therapy[J]. Journal of the American Chemical Society, 2004, 126(34):10619-10631.
[18] McDonnell S O, Hall M J, Allen L T, et al. Supramolecular photonic therapeutic agents[J]. Journal of the American Chemical Society, 2005, 127(47):16360-16361.
[19] Donyagina V F, Shimizu S, Kobayashi N, et al. Synthesis of N,N-difluoroboryl complexes of 3,3'-diarylazadiisoindolylmethenes[J]. Tetrahedron Letters, 2008, 49:6152-6154.
[20] Zhao W, Carreira E M. Conformationally restricted aza-BODIPY:Highly fluorescent, stable near-infrared absorbing dyes[J]. Chemistry:A European Journal, 2006, 12(27):7254-7263.
[21] Hall M J, Allen L T, O'Shea D F. PET modulated fluorescent sensing from the BF₂ chelated azadipyrromethene platform[J]. Organic & Biomolecular Chemistry, 2006, 4(5):776-780.
[22] Killoran J, O'Shea D F. Impact of a conformationally restricted receptor on the BF₂ chelated azadipyrromethene fluorosensing platform[J]. Chemical Communications, 2006, (14):1503-1505.
[23] Gawley R E, Mao H, Mahbubul Haque M, et al. Visible fluorescence chemosensor for saxitoxin[J]. The Journal of Organic Chemistry, 2007, 72(6):2187- 2191.
[24] Coskun A, Yilmaz M D, Akkaya E U. Bis(2-pyridyl)-substituted boratriazaindacene as an NIR-emitting chemosensor for Hg(Ⅱ)[J]. Optics Letters, 2007, 9(4):607-609.
[25] Loudet A, Burgess K. BODIPY dyes and their derivatives:Syntheses and spectroscopic properties[J]. Chemical Reviews, 2007, 107(11):4891-4932.
[26] Jiao L,Wu Y,Wang S,et al. Accessing near-infrared-absorbing BF₂-azadipyrromethenes via a push-pull Effect[J]. The Journal of Organic Chemistry, 2014, 79(4):1830-1835.
[27] Jiao L, Wu Y, Ding Y, et al. Conformationally restricted aza-dipyrromethene boron difluorides (aza-BODIPY) with high fluorescent quantum yields[J]. Chemistry, An Asian Journal, 2014, 9(3):805-810.
[28] Kamkaew A, Thavornpradit S, Puangsamlee T, et al. Oligoethylene glycol-substituted aza-BODIPY dyes as red emitting ER-probes[J]. Organic & Biomolecular Chemistry, 2015, 13(30):8271-8276.
[29] Kamkaew A, Burgess K. Aza-BODIPY dyes with enhanced hydrophilicity[J]. Chemical Communications, 2015, 51(53):10664-10667.
[30] Adarsh N, Krishnan M, Ramaiah D. Sensitive naked eye detection of hydrogen sulfide and nitric oxide by aza-BODIPY dyes in aqueous medium[J]. Analytical Chemistry, 2014, 86(18):9335-9342.
[31] Schutting S,Jokic T,Strobl M,et al. NIR optical carbon dioxide sensors based on highly photostable dihydroxyaza-BODIPY dyes[J]. Journal of Materials Chemistry C, 2015, 3(21):5474-5483.
[32] Liu Y, Zhu J, Xu Y, et al. Boronic acid functionalized aza-Bodipy (azaBDPBA) based fluorescence optodes for the analysis of glucose in whole blood[J]. ACS Applied Materials & Interfaces, 2015, 7(21):11141-11145.
[33] Zhang X, Yu H, Xiao Y. Replacing phenyl ring with thiophene:an approach to longer wavelength aza-dipyrromethene boron difluoride (Aza-BODIPY) dyes[J]. The Journal of Organic Chemistry, 2012, 77(1):669-673.
[34] Lu H, Shimizu S, Mack J, et al. Synthesis and spectroscopic properties of fused-ring-expanded aza-boradiazaindacenes[J]. Chemistry, An Asian Journal, 2011, 6(4):1026-1037.
[35] Liu H, Mack J, Fuo Q, et al. A selective colorimetric and fluorometric ammonium ion sensor based on the Haggregation of an aza-BODIPY with fused pyrazine rings[J]. Chemical Communications, 2011, 47(44):12092-12094.
[36] Zou B, Liu H, Mack J, et al. A new aza-BODIPY based NIR region colorimetric and fluorescent chemodosimeter for fluoride[J]. RSC Advances, 2014, 4(96):53864-53869.
[37] Jiang X D, Gao R, Yue Y, et al. A NIR BODIPY dye bearing 3,4,4a-trihydroxanthene moieties[J]. Organic & Biomolecular Chemistry, 2012, 10(34):6861-6865.
[38] Jiang X D, Xi D, Sun C, et al. Synthesis of a pyrenyl-fused aza-BODIPY as a near-infrared dye having the absorption maximum at 746 nm[J]. Tetrahedron Letters, 2015, 56(34):4868-4870.
[39] Jiang X D, Xi D, Le Guennic B, et al. Synthesis of NIR naphthyl-containing aza-BODIPY and measure of the singlet oxygen generation[J]. Tetrahedron, 2015, 71(40):7676-7680.
[40] Jiang X D, Zhang J, Shao X, et al. A selective fluorescent turn-on NIR probe for cysteine[J]. Organic & Biomolecular Chemistry, 2012, 10(10):1966-1968.
[41] Jiang X D, Zhao J, Li Q, et al. Synthesis of NIR fluorescent thienyl-containing aza-BODIPY and its application for detection of Hg²⁺:electron transfer by bonding with Hg²⁺[J]. Dyes and Pigments, 2016, 125:136-141.
[42] Zheng Q, Xu G, Prasad P N. Conformationally restricted dipyrromethene boron difluoride (BODIPY) dyes:Highly fluorescent, multicolored probes for cellular imaging[J]. Chemistry-A European Journal, 2008, 14(19):5812-5819.
[43] Wang D P, Shiraishi Y, Hirai T. A BODIPY-based fluorescent chemodosimeter for Cu(Ⅱ) driven by an oxidative dehydrogenation mechanism[J]. Chemical Communications, 2011, 47(9):2673-26765.
[44] Bura T, Pascal R, Ulrich G, et al. Highly substituted Bodipy dyes with spectroscopic features sensitive to the environment[J]. The Journal of Organic Chemistry, 2011, 76(4):1109-1117.
[45] Zhu S, Zhang J, Vegesna G, et al. Highly watersoluble neutral BODIPY dyes with controllable fluorescence quantum yields[J]. Organic Letters, 2011, 13(3):438-441.
[46] Liras M, Prieto J B, Pintado-Sierra M, et al. Synthesis, photophysical properties, and laser behavior of 3-amino and 3-acetamido BODIPY dyes[J]. Organic Letters, 2007, 9(21):4183-4186.
[47] Wang Y, Descalzo A B, Shen Z, et al. Dihydronaphthalene-fused boron-dipyrromethene (BODIPY) dyes:Insight into the electronic and conformational tuning modes of BODIPY fluorophores[J]. Chemistry-A European Journal, 2010, 16(9):2887-2903.
[48] Wang Y, Descalzo, A B, Shen Z, et al. Dihydronaphthalene-fused boron-dipyrromethene (BODIPY) dyes:Insight into the electronic and conformational tuning modes of BODIPY fluorophores[J]. Chemistry-A European Journal, 2012, 18:7306-7309.
[49] Jiang X D, Xi D, Zhao J, et al. A styryl-containing aza-BODIPY as near-infrared dye[J]. RSC Advances, 2014, 4(105):60970-60973.
[50] Wu Y, Cheng C, Jiao L J, et al. β-Thiophene-fused BF₂-azadipyrromethenes as near-infrared dyes[J]. Organic Letters, 2014, 16(3):748-751.
[51] Ulrich G, Ziessel R, Harriman A. The chemistry of fluorescent bodipy dyes:Versatility unsurpassed[J]. Angewandte Chemie (International ed. in English), 2008, 47(7):1184-1201.
[52] Loudet A, Bandichhor R, Burgess K, et al. B,O-chelated azadipyrromethenes as near-IR probes[J]. Organic Letters, 2008, 10(21):4771-4774.
[53] Jiang X D, Fu Y, Zhang T, et al. Synthesis and properties of NIR aza-BODIPY with aryl and alkynyl substituents on the boron center[J]. Tetrahedron Letters, 2012, 53(42):5703-5706.
[54] Jiang X D, Li S, Guan J, et al. Recent advances of the near-infrared fluorescent aza-BODIPY dyes[J]. Current Organic Chemistry, 2016, 20:1736-1744.
[55] Jiang X D, Guan J, Li Q, et al. New near-infrared-fluorescent aza-BODIPY dyes with 1-methyl-1H-pyrrolyl substituents at the 3,5-positions[J]. Asian Journal of Organic Chemistry, 2016, 5(8):1063-1067.
[56] Yakubovskyi V P, Shandura M P, Kovtun Y P. Pyrrolidylsubstituted azadipyrromethene with fully chelated boron atom[J]. Synthetic Communications, 2010, 40(7):944-950.
[57] Jiang X D, Li S, Le Guennic B, et al. Singlet oxygen generation properties of isometrically dibromated thienyl-containing aza-BODIPY[J]. Physical Chemistry Chemical Physics, 2016, 18(48):32686-32690.
[58] Orth K, Ruck A, Stanescu A, et al. Intraluminal treatment of inoperable oesophageal tumours by intralesional photodynamic therapy with methylene blue[J]. Lancet, 1995, 345(8948):519-520.
[59] Lu H, Mack J, Yang Y, et al. Structural modification strategies for the rational design of red/NIR region BODIPY[J]. Chemical Society Reviews, 2014, 43(13):4778-4823.
[60] Bellier Q, Pégaz S, Aronica C,et al.Near-infrared nitrofluorene substitued aza-boron-dipyrromethenes dyes[J]. Organic Letters, 2011, 13(1):22-25.
[61] Jiao L, Wu Y, Wang S, et al. Accessing near-infrared-absorbing BF₂-azadipyrromethenes via a push-pull effect[J]. The Journal of Organic Chemistry, 2014, 79(4):1830-1835.
[62] Jiang X D, Guan J, Zhao J L, et al. Synthesis, structure and photophysical properties of NIR aza-BODIPY with -F/-N₃/-NH₂ groups at 1,7-positions[J]. Dyes and Pigments, 2017, 136:619-626.
[63] Kim T, Park S, Choi Y, et al. A BODIPY-based probe for the selective detection of hypochlorous acid in living cells[J]. Chemistry-An Asian Journal, 2011, 6(6):1358-1361.
[64] Kim D, Yamamoto K, Ahn K H. A BODIPY-based reactive probe for ratio-metric fluorescence sensing of mercury ions[J]. Tetrahedron, 2012, 68:5279-5282.
[65] Ahrens J, Boöker B, Brandhorst K, et al. Sulfur-bridged BODIPY dyemers[J]. Chemistry:A European Journal, 2013, 19(34):11382-11395.
[66] Jiang X D, Liu X, Fang T, et al. Synthesis and application of methylthio-substituted BODIPY/aza-BODIPY[J]. Dyes and Pigments, 2017, 146:438-444.
[67] Gorman A, Killoran J, O'Shea C, et al. Vitro demonstration of the heavy-atom effect for photodynamic therapy[J]. Journal of the American Chemical Society, 2004, 126(34):10619-10631.
[68] Jiang X D, Kakuda K, Matsukawa S, et al. Synthesis and application of a bidentate ligand based on decafluoro-3-phenyl-3-pentanol:steric effect of pentafluoroethyl groups on the stereomutation of O-equatorial C-apical spirophosphoranes[J]. Chemistry-An Asian Journal, 2007, 2(2):314-323.
[69] Jiang X D, Matsukawa S, Yamamichi H, et al. First isolation and kinetic study of hypervalent 10-As-5 organoarsenic compounds with a C-apical, O-equatorial configuration[J]. Inorganic Chemistry, 2007, 46(14):5480-5482.
[70] Jiang X D, Matsukawa S, Kojima S, et al. Synthesis and characterization of antiapicophilic arsoranes and related compounds[J]. Inorganic Chemistry, 2012, 51(20):10996-11006.
[71] Jiang X D, Zhao J L, Xi D M, et al. A new water-soluble phosphorus-dipyrromethene and phosphorus-azadipyrromethene dye:PODIPY/aza-PODIPY[J]. Chemistry:A European Journal, 2015, 21(16):6079-6082.
[72] Jiang X D, Zhang J, Furuyama T, et al. Development of mono- and di-AcO substituted BODIPY on the boron center[J]. Organic Letters, 2012, 14(1):248-251.
[73] Jiang X D, Fang T, Liu X, et al. Synthesis of meso-CF₃-substituted BODIPY compounds with redshifted absorption[J]. European Journal of Organic Chemistry, 2017, 2017(34):5074-5079.
[74] Zheng Q, Xu G, Prasad P N. Conformationally restricted dipyrromethene boron difluoride (BODIPY) dyes:highly fluorescent, multicolored probes for cellular imaging[J]. Chemistry:A European Journal, 2008, 14(19):5812-5819.
[75] Wang D, Shiraishi Y, Hirai T. A distyryl BODIPY derivative as a fluorescent probe for selective detection of chrom-ium(Ⅲ)[J].Tetrahedron Letters, 2010, 51(18):2545-2549.
[76] Chen J, Burghart A. 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes modified for extended conjugation and restricted bond rotations[J]. The Journal of Organic Chemistry, 2000, 65(10):2900-2906.
[77] Leen V, Qin W, Yang W, et al. Synthesis, spectroscopy, crystal structure determination, and quantum chemical calculations of BODIPY dyes with increasing conformational restriction and concomitant red-shifted visible absorption and fluorescence spectra[J]. Chemistry-An Asian Journal, 2010, 5(9):2016-2026.
[78] Jiang X D, Liu X, Fang T, et al. Synthesis and photophysical properties of long wavelength absorbing BODIPY/aza-BODIPY bearing a five-membered ring[J]. Tetrahedron Letters, 2018, 59:546-549.
[79] Niu L Y, Guan Y S, Chen Y Z, et al. BODIPY-based ratiometric fluorescent sensor for highly selective detection of glutathione over cysteine and homocysteine[J]. Journal of the American Chemical Society, 2012, 134(46):18928-18931.
[80] Niu L Y, Chen Y Z, Zheng H R, et al. Design strategies of fluorescent probes for selective detection among biothiols[J]. Chemical Society Reviews, 2015, 44(17):6143-6160.
[81] Jiang X D, Yue S, Jia L, et al. NIR fluorescent azaBODIPY-based probe for the specific detection of L-Lysine[J]. Chemistr Select, 2018, 3(26):7581-7585.
[82] Kabil O, Banerjee R. Redox biochemistry of hydrogen sulfide[J]. Journal of Biological Chemistry, 2010, 285:21903-21907.
[83] Lippert A R, New E J, Chang C J. Reaction-based fluorescent probes for selective imaging of hydrogen sulfide in living cells[J]. Journal of the American Chemical Society, 2011, 133:10078-10080.
[84] Peng H, Cheng Y, Dai C, et al. A fluorescent probe for fast and quantitative detection of hydrogen sulfide in blood[J]. Angewandte Chemie International Edition, 2011, 50:9672-9675.
[85] Liu C, Pan J, Li S, et al. Capture and visualization of hydrogen sulfide by a fiuorescent probe[J]. Angewandte Chemie International Edition, 2011, 50:10327-10329.
[86] Fang T, Jiang X D, Sun C L, et al. BODIPY-based naked-eye fluorescent on-off probe with high selectivity for H₂S based on thiolysis of dinitrophenyl ether[J]. Sensors & Actuators:B. Chemical, 2019, 290:551-557.
[87] Majumdar P, Yuan X, Li S, et al. Cyclometalated Ir(Ⅲ) complexes with styryl-BODIPY ligands showing near IR absorption/emission:preparation, study of photophysical properties and application as photodynamic/luminescence imaging materials[J]. Journal of Materials Chemistry B, 2014, 2:2838-2854.
[88] Jiang X D, Zhang T J, Sun C L, et al. Synthesis of aza-BODIPY dyes bearing the naphthyl groups at 1,7-positions and application for singlet oxygen generation[J]. Chinese Chemical Letters, 2019, 30:1055-1058.
[89] Yu C, Jiao L, Hao E, et al. A family of highly fluorescent and unsymmetric bis(BF₂) chromophore containing both pyrrole and N-heteroarene derivatives:BOPPY[J]. Organic Letters, 2018, 20(15):4462-4466.
[90] Jiang X D, Yue S, Chen K P, et al. Synthesis, properties and application of novel 5,6,5,6-tetracyclic pyrazine/pyrrole-fused unsymmetric bis(BF₂) fluorescent dyes:BOPYPYs[J]. Chinese Chemical Letters, 2019, 30:2271-2273.
[91] Michel B W, Lippert A R, Chang C J. A reaction-based fluorescent probe for selective imaging of carbon monoxide in living cells using a palladium-mediated carbonylation[J]. Journal of the American Chemical Society, 2012, 134(38):15668-15671.
[92] Yang D, Wong M K, Yan Z, Regioselective intramolecular oxidation of phenols and anisoles by dioxiranes generated in situ[J]. The Journal of Organic Chemistry, 2000, 65(13):4179-4184.
[93] Yang D, Wang H L, Sun Z N, et al. A highly selective fluorescent probe for the detection and imaging of peroxynitrite in living cells[J]. Journal of the American Chemical Society, 2006, 128(18):6004-6005.
[94] Sun Z N, Wang H L, Liu F Q, et al. BODIPY-based fluorescent probe for peroxynitrite detection and imaging in living cells[J]. Organic Letters, 2009, 11(9):1887-1890.
[95] Ge Y, O'Shea F D. Azadipyrromethenes:from traditional dye chemistry to leading edge applications[J]. Chemical Society Reviews, 2016, 45(14):3846-3864.