Experimental Evaluation of CH–π Interactions in a Protein Core

Pace, Christopher J.; Kim, Diane; Gao, Jianmin

doi:10.1002/chem.201200334

Cited by 20 publications

(22 citation statements)

References 66 publications

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“…The C−H∙∙∙π interaction in benzene−methane, ethane, propane, and butane, increases monotonically from −1.1 to −2.7 kcal/mol 18–20 . The measurement of C−H∙∙∙π interactions in a cyclohexylalanine−phenylalanine pair in the core of a synthetic peptide indicates that each C−H∙∙∙π contact can contribute about −0.7 kcal/mol to peptide stability 21 . In real proteins, C−H∙∙∙π mainly occurs between an aliphatic side chain and an aromatic ring, or between two aromatic rings 14 .…”

Section: Introductionmentioning

confidence: 99%

Dissecting C−H∙∙∙π and N−H∙∙∙π Interactions in Two Proteins Using a Combined Experimental and Computational Approach

Wang

Yao

2019

Sci Rep

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C−H∙∙∙π and N−H∙∙∙π interactions can have an important contribution for protein stability. However, direct measurements of these interactions in proteins are rarely reported. In this work, we combined the mutant cycle experiments and molecular dynamics (MD) simulations to characterize C−H∙∙∙π and N−H∙∙∙π interactions and their cooperativity in two model proteins. It is shown that the average C−H∙∙∙π interaction per residue pair is ~ −0.5 kcal/mol while the N−H∙∙∙π interaction is slightly stronger. The triple mutant box measurement indicates that N−H∙∙∙π∙∙∙C−H∙∙∙π and C−H∙∙∙π∙∙∙C−H∙∙∙π can have a positive or negative cooperativity. MD simulations suggest that the cooperativity, depending on the local environment of the interactions, mainly arises from the geometric rearrangement when the nearby interaction is perturbed.

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Section: Introductionmentioning

confidence: 99%

Dissecting C−H∙∙∙π and N−H∙∙∙π Interactions in Two Proteins Using a Combined Experimental and Computational Approach

Wang

Yao

2019

Sci Rep

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“…In the last two decades, the benzene-methane complex has been used as a model system to study the CH-π interaction, which is considered to be a weak hydrogen bond 11 12 and has been found to play important roles in the physical, chemical, and biological properties of a variety of substances 13 14 15 16 17 18 19 20 . Hydrogen bonds are formed between two molecules with strongly contrasting electronegativities, one of which is terminated by a hydrogen atom 21 .…”

mentioning

confidence: 99%

Strong orbital interaction in a weak CH-π hydrogen bonding system

2016

Sci Rep

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For the first time, the intermolecular orbital interaction between benzene and methane in the benzene-methane complex, a representative of weak interaction system, has been studied by us using ab initio calculations based on different methods and basis sets. Our results demonstrate obvious intermolecular orbital interaction between benzene and methane involving orbital overlaps including both occupied and unoccupied orbitals. Similar to interatomic orbital interaction, the intermolecular interaction of orbitals forms “bonding” and “antibonding” orbitals. In the interaction between occupied orbitals, the total energy of the complex increases because of the occupation of the antibonding orbital. The existence of the CH-π hydrogen bond between benzene and methane causes a decrease in rest energy level, leading to at least −1.51 kcal/mol intermolecular interaction energy. Our finding extends the concept of orbital interaction from the intramolecular to the intermolecular regime and gives a reliable explanation of the deep orbital reformation in the benzene-methane complex.

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“…And the vertical distance of two 3-hexene is 3.47Å. 51 The MP2/6-31G (d,p) level has been used to geometry optimization of saccharide-aromatic residue systems that contain CH-p and OH-p interactions 52 and thermochemistry analysis of the p-p stacking interactions of various aromatic ring systems. 4 shows that the amplitude of bathochromic shis of the C]C stretching vibrational frequencies for 3-hexene-3hexene complexes at the offset p-p interaction mode decreased with the distance of the C9 and C27 increased from 3.27Å to 3.87Å every 0.2Å.…”

Section: Qm Calculation Results Of 3-hexene and 3-hexene-3hexene Compmentioning

confidence: 99%

The effect of POPC acyl chains packing by aromatic amino acid methyl esters investigated by ATR-FTIR combined with QM calculations

et al. 2016

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Aromatic residues play important roles in modulating the function of proteins and binding of proteins to biomembranes. However, the effect of small molecules which contain aromatic residues on the packing of unsaturated lipid acyl chains and the dynamics properties in membrane bilayers remains unclear. The membrane interactions of a series of amino acid methyl esters have been investigated to establish how different amino acids influence lipid acyl chains packing. Attenuated total reflectance-Fourier transform infrared spectroscopic (ATR-FTIR) measurements show that the ]CH and C]C stretching vibrational bands of 2-oleoyl-1-pamlitoyl-sn-glyecro-3-phosphocholine (POPC) present evident red-shifts when aromatic amino acid methyl esters are mixed into membrane bilayers. Quantum mechanical (QM) calculations further demonstrate that the red shifts of the ]CH and C]C stretching modes for POPC acyl chains are not through a direct interaction between the side chain groups and the HC]CH motif but are mainly caused by the conformational change of POPC acyl chains, in which the HC]CH motif is packed closed to the other one of an adjacent acyl chain with enhancement by dispersion interactions. The implication of these findings is that the packing of POPC acyl chains can be significantly influenced by aromatic amino acid methyl esters. This work may provide valuable insight into the effect on the lipid acyl chains packing by small molecules interacting with membranes and offer possibilities for the dynamic control of membrane fusion and binding of proteins to the membrane.

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Experimental Evaluation of CH–π Interactions in a Protein Core

Cited by 20 publications

References 66 publications

Dissecting C−H∙∙∙π and N−H∙∙∙π Interactions in Two Proteins Using a Combined Experimental and Computational Approach

Dissecting C−H∙∙∙π and N−H∙∙∙π Interactions in Two Proteins Using a Combined Experimental and Computational Approach

Strong orbital interaction in a weak CH-π hydrogen bonding system

The effect of POPC acyl chains packing by aromatic amino acid methyl esters investigated by ATR-FTIR combined with QM calculations

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