@article{taniguchi_hu_liu_du_lindsey_2018, title={Red and near-infrared fluorophores inspired by chlorophylls. Consideration of practical brightness in multicolor flow cytometry and biomedical sciences}, volume={10508}, ISSN={["1996-756X"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85047458937&partnerID=MN8TOARS}, DOI={10.1117/12.2302709}, abstractNote={Demands in flow cytometry for increased multiplexing (for detection of multiple antigens) and brightness (for detection of rare entities) require new fluorophores (i.e., “colors”) with spectrally distinct fluorescence outside the relatively congested visible spectral region. Flow cytometry fluorophores typically must function in aqueous solution upon bioconjugation and ideally should exhibit a host of photophysical features: (i) strong absorption, (ii) sizable Stokes shift, (iii) modest if not strong fluorescence, and (iv) narrow fluorescence band. Tandem dyes have long been pursued to achieve a large effective Stokes shift, increased brightness, and better control over the excitation and emission wavelengths. Here, the attractive photophysical features of chlorophylls and bacteriochlorophylls – Nature’s chosen photoactive pigments for photosynthesis – are described with regards to use in flow cytometry. A chlorophyll (or bacteriochlorophyll) constitutes an intrinsic tandem dye given the red (or near-infrared) fluorescence upon excitation in the higher energy ultraviolet (UV) or visible absorption bands (due to rapid internal conversion to the lowest energy state). Synthetic (bacterio)chlorins are available with strong absorption (near-UV molar absorption coefficient ε(λexc) ~105 M-1cm-1), modest fluorescence quantum yield (Φf = 0.05–0.30), and narrow fluorescence band (10–25 nm) tunable from 600–900 nm depending on synthetic design. The “relative practical brightness” is given by intrinsic brightness [ε(λexc) x Φf] times ηf, the fraction of the fluorescence band that is captured by an emission filter in a multicolor experiment. The spectroscopic features of (bacterio)chlorins are evaluated quantitatively to illustrate practical brightness for this novel class of fluorophores in a prospective 8-color panel.}, journal={REPORTERS, MARKERS, DYES, NANOPARTICLES, AND MOLECULAR PROBES FOR BIOMEDICAL APPLICATIONS X}, publisher={SPIE}, author={Taniguchi, Masahiko and Hu, Gongfang and Liu, Rui and Du, Hai and Lindsey, Jonathan S.}, editor={Achilefu, Samuel and Raghavachari, RameshEditors}, year={2018} } @article{zhang_reddy_mass_kim_hu_lindsey_2017, title={Synthesis of tailored hydrodipyrrins and their examination in directed routes to bacteriochlorins and tetradehydrocorrins}, volume={41}, DOI={10.1039/c7nj01892d}, abstractNote={18 gem-dimethyl stabilized hydrodipyrrins with diverse α-substituents have been prepared and examined in directed syntheses of unsymmetrically substituted hydroporphyrins.}, number={19}, journal={New Journal of Chemistry}, author={Zhang, S. F. and Reddy, M. N. and Mass, O. and Kim, H. J. and Hu, G. F. and Lindsey, Jonathan}, year={2017}, pages={11170–11189} } @article{hu_liu_alexy_mandal_bocian_holten_lindsey_2016, title={Panchromatic chromophore–tetrapyrrole light-harvesting arrays constructed from Bodipy, perylene, terrylene, porphyrin, chlorin, and bacteriochlorin building blocks}, volume={40}, ISSN={1144-0546 1369-9261}, url={http://dx.doi.org/10.1039/C6NJ01782G}, DOI={10.1039/c6nj01782g}, abstractNote={Five new chromophore–tetrapyrrole arrays bearing an ethynyl linker have been synthesized to explore the effects of chromophore nature and tetrapyrrole attachment site on panchromatic spectral properties.}, number={9}, journal={New Journal of Chemistry}, publisher={Royal Society of Chemistry (RSC)}, author={Hu, Gongfang and Liu, Rui and Alexy, Eric J. and Mandal, Amit Kumar and Bocian, David F. and Holten, Dewey and Lindsey, Jonathan S.}, year={2016}, pages={8032–8052} } @article{amanpour_hu_alexy_mandal_kang_yuen_diers_bocian_lindsey_holten_2016, title={Tuning the Electronic Structure and Properties of Perylene-Porphyrin-Perylene Panchromatic Absorbers}, volume={120}, ISSN={["1089-5639"]}, DOI={10.1021/acs.jpca.6b06857}, abstractNote={Light-harvesting architectures that afford strong absorption across the near-ultraviolet to near-infrared region, namely, panchromatic absorptivity, are potentially valuable for capturing the broad spectral distribution of sunlight. One previously reported triad consisting of two perylene monoimides strongly coupled to a free base porphyrin via ethyne linkers (FbT) shows panchromatic absorption together with a porphyrin-like S1 excited state albeit at lower energy than that of a typical monomeric porphyrin. Here, two new porphyrin-bis(perylene) triads have been prepared wherein the porphyrin bears two pentafluorophenyl substituents. The porphyrin is in the free base (FbT-F) or zinc chelate (ZnT-F) forms. The zinc chelate (ZnT) of the original triad bearing nonfluorinated aryl rings also was prepared. The triads were characterized using static and time-resolved optical spectroscopy. The results were analyzed with the aid of molecular-orbital characteristics obtained using density functional theory calculations. Of the four triads, FbT is the most panchromatic in affording the most even distribution of absorption spectral intensity as well as exhibiting the largest wavelength span (380-750 nm). The triads exhibit fluorescence yields (0.35 for FbT-F in toluene) that are substantially greater than for the porphyrin benchmarks (0.049 for FbP-F). The singlet excited-state lifetimes (τS) for the triads in toluene decrease in the order FbT-F (2.7 ns) > FbT (2.0 ns) > ZnT (1.2 ns) ∼ ZnT-F (1.1 ns). The τS values in benzonitrile are FbT (1.3 ns) > FbT-F (1.2 ns) > ZnT-F (0.6 ns) > ZnT (0.2 ns). Thus, the free base triads exhibit relatively long (1.2-2.7 ns) excited-state lifetimes in both polar and nonpolar media. The combined photophysical characteristics indicate that FbT and FbT-F are the best choices for panchromatic light-harvesting systems. Collectively, the findings afford insights into the effects of electronic structure on the panchromatic behavior of ethynyl-linked porphyrin-perylene architectures that can help guide next-generation designs and utilization of these systems.}, number={38}, journal={JOURNAL OF PHYSICAL CHEMISTRY A}, author={Amanpour, Javad and Hu, Gongfang and Alexy, Eric J. and Mandal, Amit Kumar and Kang, Hyun Suk and Yuen, Jonathan M. and Diers, James R. and Bocian, David F. and Lindsey, Jonathan S. and Holten, Dewey}, year={2016}, month={Sep}, pages={7434–7450} } @article{hu_hu_crawford_gorman_2013, title={Comparison of the growth and degradation of Poly(glycolic acid) and Poly(epsilon-caprolactone) brushes}, volume={51}, number={21}, journal={Journal of Polymer Science. Part A, Polymer Chemistry}, author={Hu, X. F. and Hu, G. F. and Crawford, K. and Gorman, C. B.}, year={2013}, pages={4643–4649} }