Reaction-based BODIPY probes for selective bio-imaging

Complex intracellular environment of cells, which involves interaction of a large variety of bio-molecules, is a dynamic medium with full of important information that can be recovered as well as many unanswered questions. It is highly critical to image and track biologically relevant molecules in their native media without interfering with the regular cellular processes in order to gather as much data as possible to illuminate intricacies of the biological mechanisms. To that end, small-molecule fluorescent probes have been extensively developed during the last few decades with the help of current advances in imaging technologies. Although conventional probes utilizing non-covalent supramolecular interactions with the analyte of interest are successful, significant effort has been also put into the design of reaction-based probes (chemodosimeters). Chemodosimeters exploit selective reactions of analytes with fluorophores in attempt to improve the selectivity of the probes, address the limitations of former sensors and broaden the palette of useful probes. Various types of fluorophore scaffolds can be used in the design of chemodosimeters for visualization of different analytes. In this review, we highlight the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) based chemodosimeters which have been used to image bio-thiols, reactive oxygen/nitrogen species, and gaseous molecules in living cells. © 2017 Elsevier B.V

Atropisomeric Dyes: Axial Chirality in Orthogonal BODIPY Oligomers

Cataloged from PDF version of article.A dissymmetrically substituted orthogonal BODIPY dimer and an orthogonal BODIPY trimer exist as two stable conformers, which are in fact atropisomeric enantiomers. The racemic mixture can be separated by HPLC using a chiral stationary phase. These enantiomeric derivatives hold great potential as chiral agents in asymmetric synthesis, fluorogenic/chromogenic sensing, and biological applications

Synthesis and dye sensitized solar cell applications of Bodipy derivatives with bis-dimethylfluorenyl amine donor groups

Three Bodipy dyes with strong absorptivities in the visible and near infrared regions were designed, synthesized and their potential as photosensitizers for liquid electrolyte-based dye sensitized solar cells have been evaluated. For the first time Bodipy derivatives with bis-dimethylfluorenyl amine donor groups which were known for their bulky structures as donor groups have been used together. We altered our mostly used triphenylamine group with these and investigated the dye-sensitized solar cell efficiencies of this new class of Bodipy dyes. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2015

Chromogenic and Fluorogenic Sensing of Biological Thiols in Auqeous Solutions Using BODIPY-Based Reagents

Cataloged from PDF version of article.udicious design of BODIPY dyes carrying nitroethenyl substituents in conjugation with the BODIPY core yields dyes that respond to biological thiols by both absorbance and emission changes. Incorporation of solubilizing ethyleneglycol units ensures water solubility. The result is bright signaling of biologically relevant thiols in the longer wavelength region of the visible spectrum and in aqueous solutions

Design and synthesis of soluble dibenzosuberane-substituted fullerene derivatives for bulk-heterojunction polymer solar cells

Cataloged from PDF version of article.Two new dibenzosuberane-substituted fullerene derivatives, dibenzosuberane-C60 monoadduct (DBSCMA) and bis-adduct (DBSCBA) were synthesized using a classical cyclopropanation reaction via a tosylhydrazone route for application as acceptor materials in polymer solar cells (PSCs). DBSCBA shows good solubility in common organic solvents and both derivatives were characterized by 1HNMR, 13C NMR, MALD-TOF, elemental analysis and UV-vis absorption measurements. The shift of fullerene energy levels induced by the dibenzosuberane substitution was investigated by using theoretical simulations and ultraviolet photoelectron spectroscopy. Bulk-heterojunction PSCs based on poly (3-hexylthiophene) (P3HT) and dibenzosuberane-C60 derivatives were fabricated and optimized by adjusting the donor/acceptor ratio and using thermal annealing and solvent additive. The morphologies of the active layers processed under different conditions were also examined by atomic force microscopy. When tested under an illumination of AM 1.5 G at 100 mW/ cm2, the highest power conversion efficiency of the devices using DBSCBA is 3.70% which is superior to that of conventional P3HT:PCBM devices. © 2013 Elsevier B.V

Activatable Photosensitizers: Agents for Selective Photodynamic Therapy

Recent developments in the design of bifunctional and activatable photosensitizers rejuvenate the aging field of photodynamic sensitization and photodynamic therapy. While systematic studies have uncovered new dyes that can serve as potential photosensitizers, the most promising results have come from studies aimed at gaining precise control over the location and rate of cytotoxic singlet oxygen generation. As a consequence, higher selectivities and efficiencies in photodynamic treatment protocols are now within reach. This feature article highlights the variety of approaches that have been pursued to improve photodynamic therapy and to transform simple photosensitizers into smarter theranostic agents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

Tetrastyryl-bodipy dyes: Convenient synthesis and characterization of elusive near IR fluorophores

1,3,5,7-Tetramethyl-Bodipy derivatives undergo Knoevenagel-type condensations with aromatic aldehydes to ultimately yield tetrastyryl-Bodipy derivatives. The resulting dyes absorb and emit strongly In the near IR. As the versatility of the Bodipy dyes are fully appreciated, these new tetrastyryl dyes are likely to be featured In a variety of functional supramolecular systems. © 2009 American Chemical Society

Heavy atom free singlet oxygen generation: Doubly substituted configurations dominate S 1 states of bis-BODIPYs

S 0, S 1, and T 1 states of various orthogonal 8,8′ and 8,2′-bis-boradiaza-s-indacene (BODIPY) dyes, recently (Angew. Chem., Int. Ed.2011, 50, 11937) proposed as heavy atom free photosensitizers for O 2( 1Δ g) generation, were studied by multireference quantum chemical approaches. S 0→S 1 excitation characteristics of certain bis-BODIPYs are shown to be drastically different than the parent BODIPY chromophore. Whereas a simple HOMO→LUMO-type single substitution perfectly accounts for the BODIPY core, S 1 states of certain orthogonal bis-BODIPYs are described as linear combinations of doubly substituted (DS) configurations which overall yield four electrons in four singly occupied orbitals. Computed DS character of S 1, strongly correlated with facile 1O 2 production, was presumed to occur via S 1→T 1 intersystem crossing (ISC) of the sensitizer. Further confirmation of this relation was provided by newly synthesized BODIPY derivatives and comparison of spectroscopic properties of their dimers and monomers. Near-IR absorption, desired for potential photodynamic therapy applications, was not pursuable for bis-chromophores by the standard strategy of π-extension, as DS singlet states are destabilized. Decreased exchange coupling in π-extended cases appears to be responsible for this destabilization. Comparisons with iodine incorporated bis-BODIPYs suggest that the dynamics of 1O 2 generation via DS S 1 states are qualitatively different from that via ISC originating from heavy atom spin-orbit coupling. Although red-shifting the absorption wavelength to enter the therapeutic window does not seem attainable for orthogonal bis-BODIPYs with DS S 1 states, modifications in the chromophore cores are shown to be promising in fine-tuning the excitation characteristics. © 2012 American Chemical Society

Designing Excited States: Theory-Guided Access to Efficient Photosensitizers for Photodynamic Action

Cataloged from PDF version of article.The in silico design of tetraradical S 1 states was validated experimentally through synthesis, followed by characterization including phosphorescence measurements, use of trap molecules, and cell culture studies, leading to a series of orthogonal dimers of Bodipy chromophores with remarkable singlet oxygen efficiencies (see picture). A new path for the rational development of efficient photosensitizers is thus revealed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Optimization of distyryl-Bodipy chromophores for efficient panchromatic sensitization in dye sensitized solar cells

Cataloged from PDF version of article.Versatility of Bodipy (4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene) dyes was further expanded in recent dye-sensitized solar cell applications. Here we report a series of derivatives designed to address earlier problems in Bodipy sensitized solar cells. In the best case example, an overall efficiency of a modest 2.46% was achieved, but panchromatic nature of the dyes is quite impressive. This is the best reported efficiency in liquid electrolyte solar cells with Bodipy dyes as photosensitizers