Self-Assembly of a Molecular Capsule Driven by Electrostatic Interaction in Aqueous Solution

Hamelin, B.; Jullien, Ludovic; Derouet, Christiane; Penhoat, C. Hervé Du; Berthault, Patrick

doi:10.1021/ja980046g

Cited by 44 publications

(30 citation statements)

References 40 publications

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“…Moreover, the hydrodynamic diameter AE ( 2 b) of CD-St can be evaluated to 2 nm by analogy with hydrodynamic measurements that have been performed on other b-cyclodextrin derivatives. [33] Therefore, the length of the ellipsoid L 2 a is found to be 3.5 nm. The obtained L value compares well to the Quanta molecular model of the complex as in Figure 9b since the height of one CD-St molecule was evaluated to 1.7 nm.…”

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confidence: 91%

Photophysical and Structural Features of Inclusion Complexes with Fluorescent Dyes

1999

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The synthesis of a new watersoluble b-cyclodextrin CD-St, with seven steroidic naphthalene chromophores linked to the primary rim, is reported together with the photophysical and structural features of its inclusion complexes with merocyanine and oxazine fluorescent dyes. These complexes were formed in a buffer at pH 10. At this pH the cyclodextrin is 14 times negatively charged since each chromophore bears two carboxylic groups. No excimer emission was detected, as expected from the design principles. Two complexes can be formed with stoichiometries 1:1 and 2:1 (CD:dye) for both dyes. The respective association constants were determined. In the 2:1 complexes, the cyclodextrin secondary rims are facing each other.Such complexes are outstanding artificial antennae with 14 chromophores surrounding an energy acceptor. Comparison was made with another (previously reported) water-soluble b-cyclodextrin CD-NA with seven naphthalene chromophoresÐalso linked to the primary rimÐbut bearing only one carboxylic group each. In fact, CD-NA only forms 1:1 complexes with the same dyes. The difference in complexing ability of CD-NA and CD-St is discussed.

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confidence: 91%

Photophysical and Structural Features of Inclusion Complexes with Fluorescent Dyes

1999

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“…In particular, hepta-6-S-6-deoxy-b-CD derivatives, [35][36][37][38] which are readily synthesized from heptakis-6-iodo-6-deoxyb-CD and functional thiols, show interesting binding properties. They can form supramolecular structures including molecular capsules [39,40] and nanotubes. [31] Recently, we demonstrated the superior binding properties of hepta-6-S-6deoxy-b-CD derivatives towards the drug camptothecin, which is used for cancer treatment.…”

Section: Introductionmentioning

confidence: 99%

Recognition of Ionic Guests by Ionic β‐Cyclodextrin Derivatives

Wenz

Strassnig

Thiele

et al. 2008

Chemistry A European J

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Inclusion compounds of cationic, anionic, and neutral p-substituted derivatives of tert-butylbenzene complexed in beta-cyclodextrin and its ionic 6-mono and 6-hepta derivatives were systematically investigated by isothermal titration calorimetry (ITC). All inclusion compounds showed 1:1 stoichiometry with binding constants ranging from 10 to 3 x 10(6) M(-1). The binding free energies could be subdivided into apolar and electrostatic contributions. The electrostatic interactions could be quantitatively described by Coulomb's law by taking into account the degree of protonation of hosts and guests, the orientations of the guests within the hosts, and ion shielding as described by the Debye-Hückel-Onsager theory. The orientations of the guests within the cyclodextrin cavities were determined by ROESY NMR spectroscopy.

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“…Advanced NMR techniques, in combination with MD simulations, are most promising for this purpose, despite the fact that the time scale of the NMR experiments only allows for generation of average structural and dynamics descriptors. Although vicinal coupling 3 J C,H couplings, and the nuclear Overhauser effect (nOe) provide valuable information, on the average, NMR relaxation times15, 16 and field gradient experiments4, 17 give significant information about the dynamics properties of the solutes in solution 18–21. One important limitation of this combined molecular modeling approach is that carbohydrates are especially difficult to model22 due to their highly polar functionality, their flexibility and the differences in electronic arrangements that occur during conformational and configurational changes, such as the anomeric, exo‐anomeric and gauche effects.…”

Section: Introductionmentioning

confidence: 99%

A hydration study of (1→4) and (1→6) linked α‐glucans by comparative 10 ns molecular dynamics simulations and 500‐MHz NMR

et al. 2004

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The hydration behavior of two model disaccharides, methyl-alpha-D-maltoside (1) and methyl-alpha-D-isomaltoside (2), has been investigated by a comparative 10 ns molecular dynamics study. The detailed hydration of the two disaccharides was described using three force fields especially developed for modeling of carbohydrates in explicit solvent. To validate the theoretical results the two compounds were synthesized and subjected to 500 MHz NMR spectroscopy, including pulsed field gradient diffusion measurements (1: 4.0. 10(-6) cm(2). s(-1); 2: 4.2. 10(-6) cm(2). s(-1)). In short, the older CHARMM-based force field exhibited a more structured carbohydrate-water interaction leading to better agreement with the diffusional properties of the two compounds, whereas especially the alpha-(1-->6) linkage and the primary hydroxyl groups were inaccurately modeled. In contrast, the new generation of the CHARMM-based force field (CSFF) and the most recent version of the AMBER-based force field (GLYCAM-2000a) exhibited less structured carbohydrate-water interactions with the result that the diffusional properties of the two disaccharides were underestimated, whereas the simulations of the alpha-(1-->6) linkage and the primary hydroxyl groups were significantly improved and in excellent agreement with homo- and heteronuclear coupling constants. The difference between the two classes of force field (more structured and less structured carbohydrate-water interaction) was underlined by calculation of the isotropic hydration as calculated by radial pair distributions. At one extreme, the radial O em leader O pair distribution function yielded a peak density of 2.3 times the bulk density in the first hydration shell when using the older CHARMM force field, whereas the maximum density observed in the GLYCAM force field was calculated to be 1.0, at the other extreme.

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Self-Assembly of a Molecular Capsule Driven by Electrostatic Interaction in Aqueous Solution

Cited by 44 publications

References 40 publications

Photophysical and Structural Features of Inclusion Complexes with Fluorescent Dyes

Photophysical and Structural Features of Inclusion Complexes with Fluorescent Dyes

Recognition of Ionic Guests by Ionic β‐Cyclodextrin Derivatives

A hydration study of (1→4) and (1→6) linked α‐glucans by comparative 10 ns molecular dynamics simulations and 500‐MHz NMR

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