title: Bioinspired Molecular Lantern: Tuning the Firefly Oxyluciferin Emission with Host-Guest Chemistry.
abstract: Fireflies generate flashes of visible light via luciferase-catalyzed chemiexcitation of the substrate (luciferin) to the first excited state of the emitter (oxyluciferin). Microenvironment effects are often invoked to explain the effects of the luciferase active pocket on the emission; however, the exceedingly complex spectrochemistry and synthetic burdens have precluded elucidation of the nature of these interactions. To decipher the effects of microenvironment on the light emission, here the hydrophobic interior of cucurbit[7]uril (CB7) is used to mimic the nonpolar active pocket of luciferase. The hydrophobic interior of CB7 induces shifts of the ground-state pKas by 1.9-2.5 units to higher values. Upon sequestration, the emission maxima of neutral firefly oxyluciferin and its conjugate monodeprotonated base are blue-shifted by 40 and 39 nm, respectively, resulting in visual color changes of the emitted light.
authors.affiliation: Department of Chemistry, College of Science, United Arab Emirates University , P. O. Box 15551, Al Ain, United Arab Emirates.
authors.forename: Na'il
authors.initials: N
authors.lastname: Saleh
authors.affiliation: Department of Chemistry, College of Science, United Arab Emirates University , P. O. Box 15551, Al Ain, United Arab Emirates.
authors.forename: Abdul Rahman Ba
authors.initials: AR
authors.lastname: Suwaid
authors.affiliation: Department of Chemistry, College of Science, United Arab Emirates University , P. O. Box 15551, Al Ain, United Arab Emirates.
authors.forename: Ahmad
authors.initials: A
authors.lastname: Alhalabi
authors.affiliation: Department of Chemistry, College of Science, United Arab Emirates University , P. O. Box 15551, Al Ain, United Arab Emirates.
authors.forename: Ahmed Z A
authors.initials: AZ
authors.lastname: Abuibaid
authors.affiliation: Department Chemie, Technische Universität München , Lichtenbergstrasse 4, 85748 Garching bei München, Germany.
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Maltsev
authors.affiliation: Department Chemie, Technische Universität München , Lichtenbergstrasse 4, 85748 Garching bei München, Germany.
authors.forename: Lukas
authors.initials: L
authors.lastname: Hintermann
authors.affiliation: New York University Abu Dhabi , P. O. Box 129188, Abu Dhabi, United Arab Emirates.
authors.forename: Panče
authors.initials: P
authors.lastname: Naumov
mesh_terms: D000818:Animals; D001952:Bridged-Ring Compounds / Q000737:chemistry / Q000378:metabolism; D048888:Fireflies; D049454:Firefly Luciferin / Q000737:chemistry / Q000378:metabolism; D006863:Hydrogen-Ion Concentration; D057927:Hydrophobic and Hydrophilic Interactions; D007093:Imidazoles / Q000737:chemistry / Q000378:metabolism; D007211:Indoles / Q000737:chemistry* / Q000378:metabolism; D055668:Photochemical Processes; D011719:Pyrazines / Q000737:chemistry* / Q000378:metabolism; D012996:Solutions / Q000737:chemistry; D013057:Spectrum Analysis; D047028:Macrocyclic Compounds; D000099246:Cucurbit(n)urils
chemical_list: D001952:Bridged-Ring Compounds; D049454:Firefly Luciferin; D007093:Imidazoles; D007211:Indoles; D011719:Pyrazines; D012996:Solutions; C456276:cucurbit(7)uril; D047028:Macrocyclic Compounds; D000099246:Cucurbit(n)urils; C014730:oxyluciferin