Spectroscopy of tryptophan in supersonic expansions: addition of solvent molecules

Teh, C. K.; Sipior, Jeffrey; Sulkes, Mark

doi:10.1021/j100351a018

Cited by 38 publications

(34 citation statements)

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“…For a nonpolar "inert" solvent like cyclohexane, it is reasonable that an approximate mapping between solution and free jet lifetimes is given by compound rMln (ns) bIoh rjet (ns) 5-MI 9.8 0.38 18.6 indole (I) 9.0 0.33 17. 6 7-MI 7.8 0.27 15.0 3-I-acetonitrile 8 5-methoxy-I 6.9 0.43 15.3 1-MI 6.5 0.44 17.7 4-I-carboxylic acid 3.6 0.26 4 7.9 (B) 2,3-DMI 2.6 0.23 6.3 I = indole. Letters A and B denote different conformer origins in the jet-cooled sample spectra.…”

Section: Methodsmentioning

confidence: 99%

Fluorescence lifetimes of substituted indoles in solution and in free jets: evidence for intramolecular charge-transfer quenching

Arnold¹,

Tong²,

Sulkes³

1994

J. Phys. Chem.

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Fluorescence lifetime measurements for a variety of substituted indoles were taken in cyclohexane and in supersonic gas expansions. When the two data sets were compared, a strong trend became evident. Solvent polarizability effects can be seen as stabilizing intramolecular charge-transfer quenching processes in the substituted indoles that are stimulated by the correct placement of charge accepting/releasing substituents.

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Section: Methodsmentioning

confidence: 99%

Fluorescence lifetimes of substituted indoles in solution and in free jets: evidence for intramolecular charge-transfer quenching

Arnold¹,

Tong²,

Sulkes³

1994

J. Phys. Chem.

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“…A year later in 1989, Sulkes et al31 recorded the laser induced fluorescence ͑LIF͒ spectrum of the tryptophan-single water complex. Over a…”

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confidence: 99%

Zwitterion formation in hydrated amino acid, dipole bound anions: How many water molecules are required?

Xu¹,

Nilles²,

Bowen³

2003

The Journal of Chemical Physics

188

149

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While the naturally occurring amino acids are not zwitterions in the vapor phase, they are in aqueous solutions, implying that water plays an important role in inducing zwitterion formation. Together, these observations inspire the question, ''How many water molecules are required to induce zwitterion formation in a given amino acid molecule?'' In this paper, we address this question in the context of mass spectrometric and size-selected photoelectron spectroscopic studies of hydrated amino acid anions. We utilize the facts that zwitterions possess very large dipole moments, and that excess electrons can bind to strong dipole fields to form dipole bound anions, which in turn display distinctive and recognizible photoelectron spectral signatures. The appearance of dipole-bound photoelectron spectra of hydrated amino acid anions, beginning at a given hydration number, thus signals the onset of greatly enhanced dipole moments there and, by implication, of zwitterion formation. We find that five water molecules are needed to transform glycine into its zwitterion, while four each are required for phenylalanine and tryptophan. Since the excess electron may also make a contribution to zwitterion stabilization, these numbers are lower limits for how many water molecules are needed to induce zwitterion formation in these amino acids when no extra ͑net͒ charges are involved.

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“…We expect an even smaller energy gap upon complexation with more water molecules. 33 (1) a) B1 = 6-31+G*, B2 = aug-cc-pVTZ, B3 = aug-cc-pVDZ, B4 = 6-31G*; b) ref. [18].…”

Section: Resultsmentioning

confidence: 99%

“…Biomolecules cluster with solvent molecules [32,33]. Neutral complexes of amino acids and water molecules may be isolated in a matrix environment.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory study of 1:1 glycine-water complexes in the gas phase and in solution

Rao

et al. 2010

Sci. China Chem.

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We present a systematic study of 1:1 glycine-water complexes involving all possible glycine conformers. The complex geometries are fully optimized for the first time both in the gas phase and in solution using three DFT methods (B3LYP, PBE1PBE, X3LYP) and the MP2 method. We calculate the G3 energies and use them as the reference data to gauge hydrogen bond strength in the gas phase. The solvent effects are treated via the integral equation formalism-polarizable continuum model (IEF-PCM). Altogether, we locate fifty-two unique nonionized (N) structures and six zwitterionic (Z) structures in the gas phase, and fifty-five N structures and thirteen Z structures in solution. Both correlation and solvation are shown to be important in geometry determination. We found that in the gas phase, a water molecule binds more strongly to the carboxylic acid group of glycine than to its amine group, whereas in solution phase the reverse is true. The most stable Z structure is isoenergetic with the most stable N structure.National Natural Science Foundation of China [20525311, 20533030, 10774126]; Ministry of Science and Technology [2007CB815206]; Research Grants Council of Hong Kong SAR Governmen

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Spectroscopy of tryptophan in supersonic expansions: addition of solvent molecules

Cited by 38 publications

References 1 publication

Fluorescence lifetimes of substituted indoles in solution and in free jets: evidence for intramolecular charge-transfer quenching

Fluorescence lifetimes of substituted indoles in solution and in free jets: evidence for intramolecular charge-transfer quenching

Zwitterion formation in hydrated amino acid, dipole bound anions: How many water molecules are required?

Density functional theory study of 1:1 glycine-water complexes in the gas phase and in solution

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