The crystal and molecular structure of firefly <scp>D</scp>(−)-luciferin

Dennis, D.; Stanford, Richard H.

doi:10.1107/s0567740873003845

Cited by 15 publications

(16 citation statements)

References 6 publications

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“…(4) Daly (1961). (5) Dennis & Stanford (1973). (6) Gabe, Taylor, Glusker, Minkin & Patterson (1969).…”

Section: Resultsmentioning

confidence: 99%

Molecular geometry. IV. Structure of 3,4,10,11-dibenzo-1,8-diazacyclotetradeca-1,3,8,10-tetraene, a compound containing a 14-membered ring

Arora¹,

Schaefer²

1974

Acta Crystallogr Sect B

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The structure of the title compound, C20H22N2, has been determined for the purpose of elucidating the conformation of a large ring. 1098 three-dimensional intensities were measured on a Picker PDP 8/I diffractometer and the structure was refined to an R value of 0.65. The space group is P21/c with Z= 2 and a--5-02, b = 9.60, c--16.35 ,&, fl= 96"5 °. The structure was solved by the symbolic addition method.

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“…(4) Daly (1961). (5) Dennis & Stanford (1973). (6) Gabe, Taylor, Glusker, Minkin & Patterson (1969).…”

Section: Resultsmentioning

confidence: 99%

Molecular geometry. IV. Structure of 3,4,10,11-dibenzo-1,8-diazacyclotetradeca-1,3,8,10-tetraene, a compound containing a 14-membered ring

Arora¹,

Schaefer²

1974

Acta Crystallogr Sect B

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“…Remember the estimated standard deviation in the C-S bonds is 0.007 Å and in bonds involving C, N, and O is 0.01 Å. The estimated standard deviation in the bond angles at the sulfur atoms is 0.3° [ 30] . The T v and f values of the first three excited states of LH2 were calculated at TD-B3LYP/6-311++G(d,p)// CASSCF/ANO-RCC level and listed in Table 1.…”

Section: The Geometry and T V Values Of The Lh2 S 0 Statementioning

confidence: 98%

“…The B3LYP/6-31+G(d,p) calculated the PEC of LH2 Figure 1 Selected geometrical parameters (in Å or in degrees) of S 0 state of LH2 predicted by the CASSCF//ANO-RCC (in parentheses), compared with the X-ray diffraction detected values [30] , and the previous B3LYP/ 6-31+G(d) predicted values [11] (in square brackets). about the α angle from 0° to 180° (see Figure 2).…”

Section: The Geometry and T V Values Of The Lh2 S 0 Statementioning

confidence: 99%

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Ab initio investigation on the structures and spectra of the firefly luciferin

Liu

Fang

2007

Sci. China Ser. B-Chem.

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The ground state (S 0 ) geometry of the firefly luciferin (LH2) was optimized by both DFT B3LYP and CASSCF methods. The vertical excitation energies (T v ) of three low-lying states (S 1 , S 2 , and S 3 ) were calculated by TD-DFT B3LYP//CASSCF method. The S 1 geometry was optimized by CASSCF method. Its T v and the transition energy (T e ) were calculated by MS-CASPT2//CASSCF method. Both the TD-DFT and MS-CASPT2 calculated S 1 state T v values agree with the experimental one. The IPEA shift greatly affects the MS-CASPT2 calculated T v values. Some important excited states of LH2 and oxyluciferin (oxyLH2) are charge-transfer states and have more than one dominant configuration, so for deeply researching the firefly bioluminescence, the multireference calculations are desired.firefly luciferin, TD-DFT, CASSCF, CASPT2Many different organisms in nature, including bacteria, fungi, fireflies, and fishes, are endowed with the ability to emit light. The phenomenon of emitting light as a result of a chemical reaction is called chemiluminescence. When this happens in a living organism, it takes the name of bioluminescence. Bioluminescenes arise from the oxidation of an organic substrate, called luciferin (LH2), catalyzed by an enzyme called luciferase [1][2][3] . Different animals produce very different luciferins, and the specific biochemistries of bioluminescence are also different. However, one common feature to all luciferins is that they must react with molecular oxygen in order to produce light. Luciferases are oxygenases that utilize molecular oxygen to oxidize luciferins. This oxidation reaction creates a molecule in an electronically excited state. When the molecule returns to a lower electronic energy level, it returns the energy in the form of a photon of visible light [4] . The firefly is by far the most efficient example of a bioluminescent system. In fact, the quantum yield of the reaction is 0.88 [5] . Its bioluminescence process could be outlined as Scheme 1.Many aspects of this process have not yet been clearly explained; for instance, the chemical mechanism from LH2 to oxyLH2 and the chemical origin of the multiLuciferin + ATP +O 2 2 Mg luciferase + ⎯⎯⎯⎯ → oxyluciferin + AMP + PPi +CO 2 +light Scheme 1 color bioluminescence [6][7][8][9][10][11][12][13][14][15][16] . Most research on the bioluminescence of the firefly are experimental. Only a few theoretical calculations based on semi-empirical theory were reported ten years ago [9,17] . The first Density Functional Theory (DFT) calculations was done by Orlova et al. in 2003 [11] . That was quite a big step on the theoretical study on the firefly bioluminescence, and it provided some more accurate information. However, the firefly bioluminescence process is quite complicated, which is doomed to connect with some excited states. As known, DFT method is not good at calculating excited states, since it cannot optimize the geometries of excited states. We planned to study the firefly bioluminescence using multireference method. The very new paper on Nature...

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“…The structure of the pure luciferase substrate, D(-)-LH 2 , was determined about 30 years ago [97][98][99], but due to marked instability and associated impediments with purification and crystallization [100] of the real light-emitting molecule, OxyLH 2 , very little is known about its structure, and its crystal structure has not been determined until recently [101]. With consideration of only the more stable trans conformations around the C2-C2 0 bond, by means of triple chemical equilibrium (deprotonation of the two hydroxyl groups and keto-enol tautomerism of the 4-hydroxythiazole ring) OxyLH 2 can exist as six chemical forms, as shown in Fig.…”

Section: Resonance-structure Mechanismmentioning

confidence: 99%

Molecular enigma of multicolor bioluminescence of firefly luciferase

Hosseinkhani

2010

Cell. Mol. Life Sci.

152

138

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Firefly luciferase-catalyzed reaction proceeds via the initial formation of an enzyme-bound luciferyl adenylate intermediate. The chemical origin of the color modulation in firefly bioluminescence has not been understood until recently. The presence of the same luciferin molecule, in combination with various mutated forms of luciferase, can emit light at slightly different wavelengths, ranging from red to yellow to green. A historical perspective of development in understanding of color emission mechanism is presented. To explain the variation in the color of the bioluminescence, different factors have been discussed and five hypotheses proposed for firefly bioluminescence color. On the basis of recent results, light-color modulation mechanism of firefly luciferase propose that the light emitter is the excited singlet state of OL(-) [(1)(OL(-))*], and light emission from (1)(OL(-))* is modulated by the polarity of the active-site environment at the phenol/phenolate terminal of the benzothiazole fragment in oxyluciferin.

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The crystal and molecular structure of firefly D(−)-luciferin

Cited by 15 publications

References 6 publications

Molecular geometry. IV. Structure of 3,4,10,11-dibenzo-1,8-diazacyclotetradeca-1,3,8,10-tetraene, a compound containing a 14-membered ring

Molecular geometry. IV. Structure of 3,4,10,11-dibenzo-1,8-diazacyclotetradeca-1,3,8,10-tetraene, a compound containing a 14-membered ring

Ab initio investigation on the structures and spectra of the firefly luciferin

Molecular enigma of multicolor bioluminescence of firefly luciferase

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