Microsolvation of the acetanilide cation (AA+) in a nonpolar solvent: IR spectra of AA+–Lnclusters (L = He, Ar, N2; n ≤ 10)

Schmies, Matthias; Patzer, A. B. C.; Schütz, Markus; Miyazaki, Mitsuhiko; Fujii, Masaaki; Dopfer, Otto

doi:10.1039/c4cp00401a

Cited by 26 publications

(30 citation statements)

References 72 publications

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“…[9,44,53,60,[69][70][71][72][73][74][75][76][77][78][79][80][81] It rests on aq uadrupole-octopole-quadrupole tandem mass spectrometer combined with an electron ionization source. PEA was introduced into the gas phase by heating the liquid sample purchased from Sigma Aldrich (> 99.5 %) to 330 K and seeding its vapor into Ne (12 bar) or Ar (5 bar) carrier gas.…”

Section: Methodsmentioning

confidence: 99%

Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate

2015

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Hydration has a drastic impact on the structure and function of flexible biomolecules, such as aromatic ethylamino neurotransmitters. The structure of monohydrated protonated phenylethylamine (H(+) PEA-H2 O) is investigated by infrared photodissociation (IRPD) spectroscopy of cold cluster ions by using rare-gas (Rg=Ne and Ar) tagging and dispersion-corrected density functional theory calculations at the B3LYP-D3/aug-cc-pVTZ level. Monohydration of this prototypical neurotransmitter gives an insight into the first step of the formation of its solvation shell, especially regarding the competition between intra- and intermolecular interactions. The spectra of Rg-tagged H(+) PEA-H2 O reveal the presence of a stable insertion structure in which the water molecule is located between the positively charged ammonium group and the phenyl ring of H(+) PEA, acting both as a hydrogen bond acceptor (NH(+) ⋅⋅⋅O) and donor (OH⋅⋅⋅π). Two other nearly equivalent isomers, in which water is externally H bonded to one of the free NH groups, are also identified. The balance between insertion and external hydration strongly depends on temperature.

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Section: Methodsmentioning

confidence: 99%

Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate

2015

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“…Recent applications of this IRPD approach of tagged ions in our laboratory include hydrocarbon ions, [48][49][50][51][52][53][54][55][56][57] silicon-containing ions, [58][59][60] and biological molecules and their hydrates. [61][62][63][64][65][66] DFT calculations 67 are carried out at the B3LYP-D3/aug-cc-pVTZ level to determine the geometric, vibrational, and energetic properties of the H + PEA conformers and their H + PEA-Rg n clusters. The Grimme dispersion correction 68 is used to accurately describe the dispersion forces, which are particularly relevant for the intermolecular bonds to the Rg atoms and the intramolecular NH + -p interaction of H + PEA.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH₃⁺–π interaction

Bouchet

Schütz

Chiavarino

et al. 2015

Phys. Chem. Chem. Phys.

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The structure and dynamics of the highly flexible side chain of (protonated) phenylethylamino neurotransmitters are essential for their function. The geometric, vibrational, and energetic properties of the protonated neutrotransmitter 2-phenylethylamine (H(+)PEA) are characterized in the N-H stretch range by infrared photodissociation (IRPD) spectroscopy of cold ions using rare gas tagging (Rg = Ne and Ar) and anharmonic calculations at the B3LYP-D3/(aug-)cc-pVTZ level including dispersion corrections. A single folded gauche conformer (G) protonated at the basic amino group and stabilized by an intramolecular NH(+)-π interaction is observed. The dispersion-corrected density functional theory calculations reveal the important effects of dispersion on the cation-π interaction and the large vibrational anharmonicity of the NH3(+) group involved in the NH(+)-π hydrogen bond. They allow for assigning overtone and combination bands and explain anomalous intensities observed in previous IR multiple-photon dissociation spectra. Comparison with neutral PEA reveals the large effects of protonation on the geometric and electronic structure.

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“…Examples for case b include the large and fundamental class of clusters composed of nonpolar ligand atoms and molecules [L = rare gas (Rg) atoms, N 2 , O 2 , CH 4 , etc.] and acidic aromatic solute molecules with OH and NH functional groups (e.g., phenols, anilines, indoles). ,,− In these clusters, the π-bonded global minimum in the S 0 state is only a local minimum in the D 0 state, in which the OH···L or NH···L H-bonded structure is most stable. While the interaction in the neutral cluster is dominated by dispersion (preferring π-stacking), it is dominated by induction in the ionic cluster (preferring H-bonding), leading to an ionization-induced π → H switch in the preferred ion–ligand recognition motif (Figure a) .…”

Section: Introductionmentioning

confidence: 99%

Probing Solvation Dynamics around Aromatic and Biological Molecules at the Single-Molecular Level

2016

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Solvation processes play a crucial role in chemical reactions and biomolecular recognition phenomena. Although solvation dynamics of interfacial or biological water has been studied extensively in aqueous solution, the results are generally averaged over several solvation layers and the motion of individual solvent molecules is difficult to capture. This review describes the development and application of a new experimental approach, namely, picosecond time-resolved pump-probe infrared spectroscopy of size- and isomer-selected aromatic clusters, in which for the first time the dynamics of a single individual solvent molecule can be followed in real time. The intermolecular isomerization reaction is triggered by resonant photoionization (pump), and infrared photodissociation (probe) at variable delay generates the spectroscopic signature of salient properties of the reaction, including rates, yields, pathways, branching ratios of competing reactions, existence of reaction intermediates, occurrence of back reactions, and time scales of energy relaxation processes. It is shown that this relevant information can reliably be decoded from the experimental spectra by sophisticated molecular dynamics simulations. This review covers a description of the experimental strategies and spectroscopic methods along with all applications to date, which range from aromatic clusters with nonpolar solvent molecules to aromatic monohydrated biomolecules.

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Microsolvation of the acetanilide cation (AA⁺) in a nonpolar solvent: IR spectra of AA⁺–L_nclusters (L = He, Ar, N₂; n ≤ 10)

Cited by 26 publications

References 72 publications

Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate

Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate

IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH₃⁺–π interaction

Probing Solvation Dynamics around Aromatic and Biological Molecules at the Single-Molecular Level

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Microsolvation of the acetanilide cation (AA+) in a nonpolar solvent: IR spectra of AA+–Lnclusters (L = He, Ar, N2; n ≤ 10)

Cited by 26 publications

References 72 publications

Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate

Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate

IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH3+–π interaction

Probing Solvation Dynamics around Aromatic and Biological Molecules at the Single-Molecular Level

Contact Info

Product

Resources

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Microsolvation of the acetanilide cation (AA⁺) in a nonpolar solvent: IR spectra of AA⁺–L_nclusters (L = He, Ar, N₂; n ≤ 10)

IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH₃⁺–π interaction