Supramolecular influence on cis–trans isomerization probed by ion mobility spectrometry

Czerwinska, Izabella; Kulesza, Alexander; Choi, Chang Min; Chirot, Fabien; Simon, Anne-Laure; Far, Johann; Kune, Christopher; Pauw, Edwin De; Dugourd, Philippe

doi:10.1039/c6cp06168k

Cited by 18 publications

(18 citation statements)

References 31 publications

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“…As examples, a single water molecule was found to shift the absorption spectrum of the highly symmetric MnO 4 − ion by only 0.01 eV, while a shift of 0.2 eV was measured for the (intrinsic) CT‐transition of meta ‐nitrophenolate . Recent work by Dugourd and co‐workers also showed that a methylpyridinium derivative experiences a shift in absorption by 0.4 eV upon complexation with 18‐crown‐6 ether in agreement with the strong intrinsic CT character of the transition. Finally, beautiful evidence for the importance of the character of the excited state was reported by Jouvet and co‐workers: The absorption by protonated polycyclic aromatic hydrocarbons (PAHs) does not simply redshift with molecular size as it does for the neutral analogues.…”

Section: Figuresupporting

confidence: 84%

Accessing the Intrinsic Nature of Electronic Transitions from Gas‐Phase Spectroscopy of Molecular Ion/Zwitterion Complexes

et al. 2017

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A molecule's color is governed by the nature of its electronic transitions. Herein we show that the degree of charge transfer can be assessed by measuring the change in absorption induced by complexation with the betaine zwitterion. Our approach benefits from direct formation of complexes by electrospray of a mixture solution, followed by photodissociation action spectroscopy. We explored two ion groups: 1) No permanent dipole moment due to even charge delocalization (e.g. MnO4−) and 2) Non‐even charge distribution but where the charge according to resonance forms is either delocalized (e.g. oxyluciferin) or located at one site (e.g. m‐nitrophenolate, mNP). The maximal shift for ions from (1) was <0.05 eV but as large as 0.3 eV and 0.2 eV for mNP and oxyluciferin. Hence our work supports the notion that oxyluciferin undergoes CT, and that the microenvironment can account for large variation in light emission from insects, ranging from green to red (shift of 0.3 eV).

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Section: Figuresupporting

confidence: 84%

Accessing the Intrinsic Nature of Electronic Transitions from Gas‐Phase Spectroscopy of Molecular Ion/Zwitterion Complexes

et al. 2017

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“…[13] As examples,asingle water molecule was found to shift the absorption spectrum of the highly symmetric MnO 4 À ion by only 0.01 eV, [9] while as hift of 0.2 eV was measured for the (intrinsic) CT-transition of meta-nitrophenolate. [8] Recent work by Dugourd and co-workers [14] also showed that am ethylpyridinium derivative experiences as hift in absorption by 0.4 eV upon complexation with 18-crown-6 ether in agreement with the strong intrinsic CT character of the transition. Finally,b eautiful evidence for the importance of the character of the excited state was reported by Jouvet and co-workers: [15] Thea bsorption by protonated polycyclic aromatic hydrocarbons (PAHs) does not simply redshift with molecular size as it does for the neutral analogues.…”

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confidence: 79%

Accessing the Intrinsic Nature of Electronic Transitions from Gas‐Phase Spectroscopy of Molecular Ion/Zwitterion Complexes

et al. 2017

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A molecule's color is governed by the nature of its electronic transitions. Herein we show that the degree of charge transfer can be assessed by measuring the change in absorption induced by complexation with the betaine zwitterion. Our approach benefits from direct formation of complexes by electrospray of a mixture solution, followed by photodissociation action spectroscopy. We explored two ion groups: 1) No permanent dipole moment due to even charge delocalization (e.g. MnO ) and 2) Non-even charge distribution but where the charge according to resonance forms is either delocalized (e.g. oxyluciferin) or located at one site (e.g. m-nitrophenolate, mNP). The maximal shift for ions from (1) was <0.05 eV but as large as 0.3 eV and 0.2 eV for mNP and oxyluciferin. Hence our work supports the notion that oxyluciferin undergoes CT, and that the microenvironment can account for large variation in light emission from insects, ranging from green to red (shift of 0.3 eV).

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“…Our collaboration has also studied these proteins by means of IMS and IR spectroscopy . Recently, tandem IMS emerged as a technique allowing to select a conformer of a given molecular ion of controlled m / z ratio, activate it by low‐energy collisions or laser photoabsorption, and monitor the induced structural changes …”

Section: Figurementioning

confidence: 99%

“…[21] Recently,t andem IMS emerged as at echnique allowing to select ac onformer of ag iven molecular ion of controlled m/ z ratio, activate it by low-energy collisions or laser photoabsorption, and monitorthe induced structural changes. [22][23][24][25][26][27][28] In this work, we report the results of experiments using tandem IMS coupled to mass spectrometry,a pplied to the investigation of the structure ands tability of CMP in the gas phase, and give ad efinitive answer to the origin of the triple helix stabilization by hydroxyproline. Furthermore, we add insight into the requirementsf or triple-helical CMP self-assembly, which might shed light on collagen fibril growth.…”

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confidence: 99%

Isolated Collagen Mimetic Peptide Assemblies Have Stable Triple‐Helix Structures

Lalande

Comby‐Zerbino

Bouakil

et al. 2018

Chemistry A European J

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The origin of the triple-helix structure and high stability of collagen has been debated for many years. As models of the triple helix and building blocks for new biomaterials, collagen mimetic peptide (CMP) assemblies have been deeply studied in the condensed phase. In particular, it was found that hydroxylation of proline, an abundant post-translational modification in collagen, increases its stability. Two main hypotheses emerged to account for this behavior: 1) intra-helix stereoelectronic effects, and 2) the role of water molecules H-bound to hydroxyproline side-chains. However, in condensed-phase investigations, the influence of water cannot be fully removed. Therefore, we employed a combination of tandem ion mobility and mass spectrometries to assess the structure and stability of CMP assemblies in the gas phase. These results show a conservation of the structure and stability properties of triple helix models in the absence of solvent, supporting an important role of stereoelectronic effects. Moreover, evidence that small triple helix assemblies with controlled stoichiometry can be studied in the gas phase is given, which opens new perspectives in the understanding of the first steps of collagen fiber growth.

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Supramolecular influence on cis–trans isomerization probed by ion mobility spectrometry

Cited by 18 publications

References 31 publications

Accessing the Intrinsic Nature of Electronic Transitions from Gas‐Phase Spectroscopy of Molecular Ion/Zwitterion Complexes

Accessing the Intrinsic Nature of Electronic Transitions from Gas‐Phase Spectroscopy of Molecular Ion/Zwitterion Complexes

Accessing the Intrinsic Nature of Electronic Transitions from Gas‐Phase Spectroscopy of Molecular Ion/Zwitterion Complexes

Isolated Collagen Mimetic Peptide Assemblies Have Stable Triple‐Helix Structures

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