Here we formulate equations based solely on empirical Hammett substituent constants to predict the redox potentials for the electronic excited state of boron-dipyrromethene (BODIPY) dyes. We utilized computational, spectroscopic, and electrochemical techniques toward characterizing the effect of substitution at the positions C2, C6, and C8 of the 1,3,5,7-tetramethyl BODIPY core. Working with a library of 100 BODIPY dyes, we found that highest occupied molecular orbital (HOMO) energies calculated at the B3LYP 6-31g(d) level correlated linearly with the Hammett σm value for substituents at position C8 and with Hammett σp values for substituents at positions C2 and C6. In turn, we observed that LUMO energies correlated linearly with Hammett σp at position C8 and with Hammett σm at positions C2 and C6. Focusing on a subset of 26 dyes for which reduction potentials were either previously available or measured herein and ranged from -1.84 to -0.52 V (a full 1.3 V), we found a linear relationship between redox potentials in acetonitrile and HOMO and lowest unoccupied molecule orbital (LUMO) energies determined via density functional theory (DFT). A linear correlation was thus ultimately established between redox potentials in acetonitrile and Hammett substituent constants. Combining this with equations derived for the linear relationship existing between the zero vibrational energy of the excited BODIPY and Hammett substituent constants enabled us to provide the parameters toward predicting the oxidizing/reducing power of photoexcited 1,3,5,7,-tetramethyl BODIPY dyes in their singlet excited state.
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http://dx.doi.org/10.1021/jp5059148 | DOI Listing |
Microorganisms
December 2024
Advanced Institute of Convergence Technology, Suwon 16229, Republic of Korea.
The lipid content of nine dinoflagellates was analyzed using flow cytometry to compare lipid levels. Additionally, the correlation between lipid content, cell size, and carbon content in dinoflagellates was evaluated using BODIPY 505/515 staining. The flow cytometry side scatter (SSC) effectively represented relative cell size, showing a linear relationship with the equivalent spherical diameter (ESD).
View Article and Find Full Text PDFJ Colloid Interface Sci
January 2025
Biomedical Polymers Laboratory, College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123 China; College of Pharmaceutical Sciences, Soochow University, Suzhou 215123 China. Electronic address:
Phototherapy including photothermal therapy (PTT) and photodynamic therapy (PDT) is widely used for cancer treatment because of its non-invasiveness, spatiotemporal controllability, and low side effects. However, the PTT and PDT capabilities of photosensitizers (PSs) compete so it's still a crucial challenge to simultaneously enhance the PDT and PTT capabilities of PSs. In this work, donor-π-acceptor (D-π-A)-based boron dipyrromethene (BODIPY) dyes were developed via molecular engineering and applied for enhanced phototherapy of triple-negative breast cancer.
View Article and Find Full Text PDFHere, BODIPY derivatives were functionalized with barbituric acid, which has multiple hydrogen bonding abilities that are directional, to have highly ordered hydrogen bond-mediated self-assembled structures to tune BODIPY's photophysical properties. The synthesis of barbituric acid-functionalized BODIPY derivatives via Vilsmeier and Knoevenagel reactions was achieved, and the resulting compounds were characterized with FT-IR, H NMR, C NMR spectroscopy, and mass spectrometry. Hydrogen bond-mediated self-assembled structures were investigated through UV-vis and fluorescence spectrophotometry, H NMR spectroscopy, and a dynamic light scattering method in solution.
View Article and Find Full Text PDFACS Omega
January 2025
Department of Chemistry, Middle East Technical University, 06800 Ankara, Türkiye.
This work describes the development of the first enantioselective addition reaction between 1,3,5,7-tetramethyl-BODIPYs and isatin derivatives. The reaction utilizes bifunctional quinine/squaramide organocatalysts and affords nine novel chiral BODIPY dyes under mild conditions, with enantioselectivities reaching up to 60%. The synthesized BODIPY-oxindoles exhibit high fluorescence emissions, consistent with their parent BODIPYs, and display tunable colors.
View Article and Find Full Text PDFMolecules
December 2024
Department of Chemistry and Biochemistry, Texas Christian University, Fort Worth, TX 76129, USA.
Phosphorus-containing fluorophores provide a versatile framework for tailoring photophysical properties, enabling the design of advanced fluorogenic materials for various applications. Boron dipyrromethene (BODIPY) and squaraine dyes are of interest due to their multifaceted modularity and synthetic accessibility. Incorporating phosphorus-based functional groups into BODIPY or squaraine scaffolds has been achieved through a plethora of synthetic methods, including post-dye assembly functionalization.
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