Supramolecular dynamics

Bohne, Cornelia

doi:10.1039/c3cs60352k

Cited by 105 publications

(116 citation statements)

References 44 publications

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“…13 The objective of the present study was to determine how hydrophobic and hydrophilic substituents affect the OA-guest capsule dynamics and how these changes are related to the overall stability of the capsule; to accomplish this we used stopped-flow fluorescence experiments to circumnavigate the issue that kinetic pathways cannot be inferred from the determination of equilibrium constants. 20 …”

mentioning

confidence: 99%

Tuning the Binding Dynamics of a Guest–Octaacid Capsule through Noncovalent Anchoring

Thomas

Tang

Gaudes

et al. 2017

J. Phys. Chem. Lett.

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Hydrophobic or hydrophilic substituents have different effects on the binding dynamics of pyrene derivatives with a 2:1 capsule formed from two octaacid cavitands, showing a subtle interplay of different kinetic factors. Anchoring of the methyl group of 1-methylpyrene within one cavitand slowed the association and dissociation dynamics of the 1:1 complex by at least 1,000 times when compared to the 1:1 complex for pyrene. This slow down for the transient formation of the 1:1 complex is responsible for the overall increase in stability of the 2:1 complex without affecting the overall capsule dissociation. For 1-pyrenemethanol, its residence time in the 2:1 capsule is shorter compared to pyrene despite both guests having similar equilibrium constants for the binding of the second cavitand, suggesting that the hydroxymethyl substituent close to the equatorial region of the capsule can interact with water during the partial opening of the capsule.

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mentioning

confidence: 99%

Tuning the Binding Dynamics of a Guest–Octaacid Capsule through Noncovalent Anchoring

Thomas

Tang

Gaudes

et al. 2017

J. Phys. Chem. Lett.

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“…Despite chiral recognition by CDs concerns ground state interactions and extensive investigations have been devoted in this regard [1][2][3][4][5][6][7], there is an increasing trend in the past decade towards exploring such interactions via dynamics in the excited states. The importance of these studies is related to the applications of supramolecular photochemistry in a number of intriguing key fields such as photoresolution, photochirogenisis, and photochemical asymmetric synthesis [9][10][11][12][13][14][15][16]. However, very few examples on the direct chiral recognition involving CDs or other host molecules in the excited triplet state were reported in the literature [17][18][19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Complexation and Chiral Recognition of Chiral Binaphthyl Derivatives and β-Cyclodextrins in Solution Probed by Triplet Excited State Relaxation

Riyad¹,

Laube²,

Naumov

et al. 2015

Zeitschrift Für Physikalische Chemie

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It is well known in supramolecular chemistry that cyclodextrin host molecules (CDs) are capable of including and binding guest molecules in their hydrophobic cavities via non-covalent interactions. The unique recognition capability of CDs depends on their inherent asymmetric cavities. We explored here the impacts of the chiral recognition of excited triplet state of guest 1,1 -Binaphthyl-2,2 -diylhydrogenphosphate (BNP) enantiomers by host native -cyclodextrin ( -CD) and chemically modified Heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TMe--CD). For this regard, UV-Vis, fluorescence, and laser flash photolysis spectroscopy were performed and our experimental results were flanked by density functional theory (DFT) calculations. Triplet decay dynamics of BNP enantiomers were investigated in the absence and presence of cyclodextrins under dif-1832 | Y. M. Riyad et al. ferent conditions and the chiral recognition behavior is discussed based on the obtained kinetic and spectral data of excited triplet state. Here we show that the long lived triplet excited states (as opposed to the singlet states) and its relaxation in solution may be a sensitive probe to detect chiral recognition. The ability of TMe--CD to recognize axial chirality is superior to that of -CD. These findings may be attributed to the asymmetric cavities of cyclodextrins, which determines the degree of interaction. The differences in the triplet behavior of R-and S-BNP(T 1 )-TMe--CD may arise from the different orientations of the guest molecule within the twisted and restricted TMe--CD cavity. We assume here that the orientation of the more favorable enantiomer (S-BNP(T 1 )) is geometrically preferable, while a similar orientation of the less favorable enantiomer (R-BNP(T 1 )) might be hindered by steric reasons. In contrast, the triplet dynamics of BNP enantiomers within the unrestricted macrocyclic -CD ring are similar. This might be ascribed to a similar orientation and interaction and ultimately relaxation of both enantiomers within a round and undistorted -CD cavity, suggesting the formation of similar inclusion complexes. These findings are evidence for the possibility to detect chiral recognition and interaction as well as tiny structural differences in the BNP complexes within cyclodextrin cavities via laser flash photolysis technique.

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“…) [28][29][30]39 , and their instant dissociation and re-association favors high-fidelity re-association between specific pairs of βCD and ADA, with minimal mismatching. The other structural component is the elastic chains (PDMA) formed by polymerized DMA.…”

Section: Peg-ada Hydrogels Maintain Consistent Mechanical Properties mentioning

confidence: 99%

“…The β-cyclodextrin and adamantane (βCD-ADA) host-guest complex is stable under aqueous conditions with a high-binding constant ( ) [28][29][30] . Therefore, the βCD-ADA complex is an ideal non-covalent system for mediating energy dissipation during loading and network recovery during unloading in antifatigue hydrogels.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular hydrogels cross-linked by preassembled host–guest PEG cross-linkers resist excessive, ultrafast, and non-resting cyclic compression

et al. 2018

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Poly(ethylene glycol) (PEG)-based hydrogels are promising materials for biomedical applications because of their excellent hydrophilicity and biocompatibility. However, conventional chemically cross-linked PEG hydrogels are brittle under mechanical loading. The mechanical resilience and rapid recovery abilities of hydrogel implants are critical in load-bearing tissues, such as articular cartilage, which are routinely subjected to cyclic loadings of high magnitude and frequency. Here, we report the fabrication of novel supramolecular PEG hydrogels by polymerizing N,Ndimethylacrylamide with supramolecular cross-linkers self-assembled from adamantane-grafted PEG and monoacrylated β-cyclodextrin. The resultant PEG-ADA supramolecular hydrogels exhibit substantial deformability, excellent capacity to dissipate massive amounts of loading energy, and have a rapid, full recovery during excessive, ultrafast, and non-resting cyclic compression. Furthermore, the energy dissipation capacity of the PEG-ADA (adamantane-grafted Poly(ethylene glycol)) hydrogels can be regulated by changing the concentration, molecular weight and cross-linking density of PEG. According to in vitro cell metabolism and viability tests, the PEG-ADA hydrogels are non-cytotoxic. When placed over a monolayer of myoblasts that were subjected to instantaneous compressive loading, the PEG-ADA hydrogel cushion significantly enhanced cell survival under this deleterious mechanical insult compared with the effects of the conventional PEG hydrogel. Therefore, PEG-ADA hydrogels are promising prosthetic biomaterials for the repair and regeneration of load-bearing tissues.

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Supramolecular dynamics

Cited by 105 publications

References 44 publications

Tuning the Binding Dynamics of a Guest–Octaacid Capsule through Noncovalent Anchoring

Tuning the Binding Dynamics of a Guest–Octaacid Capsule through Noncovalent Anchoring

Complexation and Chiral Recognition of Chiral Binaphthyl Derivatives and β-Cyclodextrins in Solution Probed by Triplet Excited State Relaxation

Supramolecular hydrogels cross-linked by preassembled host–guest PEG cross-linkers resist excessive, ultrafast, and non-resting cyclic compression

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