Enhanced Hydrogen Bonding Induced by Optical Excitation:  Unexpected Subnanosecond Photoinduced Dynamics in a Peptide-Based [2]Rotaxane

Wurpel, George W. H.; Brouwer, Albert M.; Stokkum, Ivo H. M. van; Farrán, M. Ángeles; Leigh, David A.

doi:10.1021/ja015919c

Cited by 94 publications

(44 citation statements)

References 10 publications

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“…The use of fluorescence for detecting the shuttling process in rotaxanes is less common. [7][8][9][10][11][12] It is well known in the field of molecular sensors that fluorescence is one of the most sensitive means of detection. [13] Moreover, fluorescence spectroscopy is very suitable for kinetic measurements with high time resolution and high dynamic range.…”

Section: Introductionmentioning

confidence: 99%

Fluorescent Perylene Diimide Rotaxanes: Spectroscopic Signatures of Wheel–Chromophore Interactions

Baggerman

Jagesar

Vallée

et al. 2007

Chemistry A European J

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[2]- and [3]-rotaxanes with a tetraphenoxy perylene diimide core were synthesized. Hydrogen bonding between the wheel and the imide changes the optical properties of the perylene chromophore: the absorption and fluorescence spectra are red-shifted. The decay times of the rotaxanes are shorter in comparison with that of the axle. Single molecule fluorescence measurements reveal relatively narrow distributions of emission maxima and decay times. The averages are in agreement with ensemble measurements. The observed red shifts make the perylene diimide a suitable chromophore for sensing the position of the wheel on the axle.

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Section: Introductionmentioning

confidence: 99%

Fluorescent Perylene Diimide Rotaxanes: Spectroscopic Signatures of Wheel–Chromophore Interactions

Baggerman

Jagesar

Vallée

et al. 2007

Chemistry A European J

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“…The synthesis and properties of rotaxanes and molecular shuttles based on various dipeptide threads and benzylic amide macrocycles have been described (4)(5)(6)(7)(8). In fact, the structural tolerance of the assembly process allows the preparation of rotaxanes derived from oligopeptide sequences of at least 2-5 amino acid residues as long as they contain at least one non-Nterminal glycine residue (9).…”

mentioning

confidence: 99%

From reactants to products via simple hydrogen-bonding networks: Information transmission in chemical reactions

Brancato

Coutrot

Leigh

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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The transmission of information is ubiquitous in nature and often occurs through supramolecular hydrogen bonding processes. Here we report that there is a remarkable correlation during synthesis between the efficiency of the hydrogen-bond-directed assembly of peptide-based [2]rotaxanes and the symmetry distortion of the macrocycle in the structure of the final product. It transpires that the ability of the flexible macrocycle-precursor to wrap around an unsymmetrical hydrogen bonding template affects both the reaction yield and a quantifiable measure of the symmetry distortion of the macrocycle in the product. When the yields of peptide rotaxane-forming reactions are high, so is the symmetry distortion in the macrocycle; when the yields are low, indicating a poor fit between the components, the macrocycle symmetry is relatively unaffected by the thread. Thus during a synthetic sequence, as in complex biological assembly processes, hydrogen bonding can code and transmit ''information''-in this case a distortion from symmetry-between chemical entities by means of a supramolecularly driven multicomponent assembly process. If this phenomenon is general, it could have far reaching consequences for the use of supramolecular-directed reactions in organic chemistry.continuous symmetry measure ͉ hydrogen bonds ͉ molecular recognition ͉ rotaxanes ͉ symmetry distortion

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“…After deprotonation (Figure 7), the relevant highlighted cross peaks relative to the loosened lasso disappear, whereas new correlation peaks demonstrate the new main localization of the macrocycle around the triazolium. In particular, new correlation peaks are observed for the hydrogens H C-H belonging to the BMP25C8 with respectively the triazolium hydrogen H 13 , the benzyl barrier H 28 28 . In a consistent way, the aromatic hydrogen H J of the BMP25C8 is correlated with H 12 , whereas the last aromatic hydrogen of the BMP25C8 H A is now correlated with H 11 .…”

Section: Studies Of the Equilibrium Between The Unthreaded Compound 1mentioning

confidence: 95%

“…They next extended their efficient five-components hydrogen bond directed clipping strategy to the synthesis and the study of a wide range of dipeptides [23][24][25][26]. They also prepared many [2]rotaxane molecular shuttles in which the encircled thread contains different peptide moieties as molecular stations [27][28][29][30][31][32][33][34][35]. Inversely, some [2]rotaxanes, in which the macrocycles consist of cyclic peptides were reported too [36].…”

Section: Introductionmentioning

confidence: 99%

A pH-Sensitive Peptide-Containing Lasso Molecular Switch

2013

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Abstract:The synthesis of a peptide-containing lasso molecular switch by a selfentanglement strategy is described. The interlocked [1] rotaxane molecular machine consists of a benzometaphenylene [25]crown-8 (BMP25C8) macrocycle surrounding a molecular axle. This molecular axle contains a tripeptidic sequence and two molecular stations: a N-benzyltriazolium and a pH-sensitive anilinium station. The tripeptide is located between the macrocycle and the triazolium station, so that its conformation can be tailored depending on the shuttling of the macrocycle from one station to the other. At acidic pH, the macrocycle resides around the anilinium moiety, whereas it shuttles around the triazolium station after deprotonation. This molecular machinery thus forces the lasso to adopt a tightened or a loosened conformation.

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Enhanced Hydrogen Bonding Induced by Optical Excitation: Unexpected Subnanosecond Photoinduced Dynamics in a Peptide-Based [2]Rotaxane

Cited by 94 publications

References 10 publications

Fluorescent Perylene Diimide Rotaxanes: Spectroscopic Signatures of Wheel–Chromophore Interactions

Fluorescent Perylene Diimide Rotaxanes: Spectroscopic Signatures of Wheel–Chromophore Interactions

From reactants to products via simple hydrogen-bonding networks: Information transmission in chemical reactions

A pH-Sensitive Peptide-Containing Lasso Molecular Switch

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