Strong binding of ditopic substrates by a doubly linked occlusive C1 clamshell as distinguished from an aversive C2 loveseat cyclodextrin dimer

Breslow, Ronald; Chung, Shin

doi:10.1021/ja00182a046

Cited by 115 publications

(52 citation statements)

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“…Quantitive correlations prove to exist and furnish insight into the nature of the interactions in some strongly bound host-guest systems. Binding constants were determined in water at -250C by fluorescence methods (5,6). For the binding of BNS (3) …”

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confidence: 99%

Quantitative effects of antihydrophobic agents on binding constants and solubilities in water.

Breslow

Halfon

1992

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

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The effects of urea and of guanidinium chloride on binding constants in water for 6-(4-tert-butylanilno)-naphthaene-2-sulfonate and of bis(p-tert-butylphenyl) phosphate binding to (3-cyclodextrin and to N,N'-bls(6--cylodextrinyl)midazolium ion have been determined. Their effects on the water solubility of p-tert-butylbenzyl alcohol and p-methylbenzyl alcohol have also been exam . Quantitative correlations show that the effects of these additives, which diminish hydrophobic effects, are similar for release of a tert-butylphenyl group from a cyclodextrin cavity into water or for solubilizing such a group from a second phase. The effects of these agents on the binding constants for double-ended substrates binding to the bis(cyclodextrin) host are much larger than for a simple substrate binding to monomeric cyclodextrin, consistent with additivity offree-energy perturbations. Ethanol also decreases binding in these systems, and increases solubilities, but the quantitative correlations are less shaightforward.Substances such as urea and guanidinium ion diminish the hydrophobic effect (for general references, see refs. 1 and 2). With proteins or nucleic acids this change leads to unfolding, so such substances are sometimes called denaturants or chaotropes; they also lead to the increased solubility of hydrophobic molecules in water, so they may be called "salting in" agents when this property is being addressed. However, they are not all salts. They have sometimes been called "water structure breakers," but previous evidence (3) indicates that they do not work primarily by breaking up water structure. Since the above properties reflect a decrease of the hydrophobic effect, we propose that such substances be called simply antihydrophobic agents.We have used such materials to diagnose the presence of hydrophobic effects in the transition states of simple organic reactions such as Diels-Alder additions and benzoin condensations (4). However, it seemed likely that more would be learned if these effects were made quantitative. That is, in any given case, one would like to know not just that a hydrophobic effect was present but also how much hydrophobic surface was involved in the effect. We have now examined the quantitative effects of antihydrophobic agents on (a) the binding constant for a tert-butylphenyl group binding in a cyclodextrin cavity, (b) the binding constant for two tert-butylphenyl groups of a double-ended substrate binding in the two cavities of a cyclodextrin dimer, and (c) the water solubility of p-tert-butylbenzyl alcohol (1) and p-methylbenzyl alcohol (2). Quantitive correlations prove to exist and furnish insight into the nature of the interactions in some strongly bound host-guest systems. MATERIALS AND METHODSUrea and guanidinium chloride were Aldrich 99+% pure and were used as supplied. Water was deionized by a commercial unit. p-tert-Butylbenzyl alcohol (Scheme 1, compound 1) and p-methylbenzyl alcohol (2) RESULTS AND DISCUSSIONThe results are listed in Table 1. As can be seen, urea, gu...

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confidence: 99%

Quantitative effects of antihydrophobic agents on binding constants and solubilities in water.

Breslow

Halfon

1992

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

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“…They have been shown to increase binding affinities significantly, yet the flexibility of a single bridge often causes that the cyclodextrin macrocycles act independently forming a complex with 2:1 stoichiometry with no enhancement in binding [17]. In contrast, cyclodextrin duplexes connected with more than one linking group are much more difficult to prepare; in fact, up until today only a few well-defined doubly [18][19][20][21][22][23] and triply [24] bridged duplexes have been reported. Two of these hosts [18,23] hold a record among cyclodextrin binary complexes with neutral organic guest molecules reaching values of K a up to 10 10 M -1 .…”

Section: Modified Cyclodextrins For Enhanced Bind-ing and Molecular Rmentioning

confidence: 99%

Modified Cyclodextrins with Pendant Cationic and Anionic Moieties as Hosts for Highly Stable Inclusion Complexes and Molecular Recognition

Kraus¹

2011

COC

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Cyclodextrins bearing pendant cationic or anionic moieties have been shown to form highly stable inclusion complexes with oppositely charged organic molecules. These charged hosts are also capable of molecular recognition of various organic cations and anions such as nucleotides and other phosphates, sulfates, sulfonates, carboxylates, enantiomers of amino acids, bile acids and many others. This review summarizes work in this field published till the year 2009 including most common synthetic methods for the preparation of charged cyclodextrin derivatives and examples of their applications in bioorganic chemistry and pharmacy.

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“…For example, certain linked dimeric b-CD species have been reported to selectively bind the hydrophobic side chain in polypeptides and modulate the polypeptide aggregation process [9]. Various guest molecules, including dyes, drugs, and steroids, have been studied for complexation and solubilization by dimeric b-CD with disulfide, bipyridine, and diamine linkers [10][11][12]. However, there is no report on the complexation of dimeric b-CD with lipids or bio-membranes.…”

Section: Introductionmentioning

confidence: 99%

Liposome solubilization induced by complexation with dimeric β-cyclodextrin

Cho

Choi

Jeong

et al. 2014

J Incl Phenom Macrocycl Chem

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Dimeric b-cyclodextrins (b-CD) were prepared from the reaction of native b-CD with epichlorohydrin under basic conditions, and the effects on the diacetylene (DA) and polydiacetylene (PDA) liposomes have been investigated. Vesicular DA was solubilized in the presence of dimeric b-CD with the consequent inhibition of polymerization. The result is attributed to the formation of a complex between dimeric b-CD and DA liposomes, and it is clearly differentiated from that of monomeric b-CD. Furthermore, the ordered supramolecular structure of PDA was perturbed by the dimeric b-CD, which was detected from the visible color change. Finally, the morphological characteristics and size of PDA in the absence and presence of dimeric b-CD were examined using transmission electron microscopy and dynamic light scattering The results show fused structure of size more than 200 nm along with the deformation of the vesicles, and they represent a novel phenomenon of liposome structure induced by complexation with dimeric b-CD. The evaluated physicochemical characteristics can be applied to the development of carbohydrate-based detergents.

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Strong binding of ditopic substrates by a doubly linked occlusive C1 clamshell as distinguished from an aversive C2 loveseat cyclodextrin dimer

Cited by 115 publications

References 1 publication

Quantitative effects of antihydrophobic agents on binding constants and solubilities in water.

Quantitative effects of antihydrophobic agents on binding constants and solubilities in water.

Modified Cyclodextrins with Pendant Cationic and Anionic Moieties as Hosts for Highly Stable Inclusion Complexes and Molecular Recognition

Liposome solubilization induced by complexation with dimeric β-cyclodextrin

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