Dendroclefts: Optically Active Dendritic Receptors for the Selective Recognition and Chiroptical Sensing of Monosaccharide Guests

Smith, David K.; Zingg, Adrien; Diederich, François

doi:10.1002/(sici)1522-2675(19990804)82:8<1225::aid-hlca1225>3.0.co;2-v

Cited by 69 publications

(24 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Specific recognition of guest molecules by dendritic hosts has been explored by Diederich and co‐workers 63–67. They developed a class of dendritic receptors, which they termed dendrophanes 63.…”

Section: Uses Of Synthetic Dendritic Structuresmentioning

confidence: 99%

“…Diederich and Smith also investigated dendritic receptors based on hydrogen bonding, called dendroclefts 66. 67 These dendrimers contained 9,9′‐spirobi[9 H ‐fluorene] cores (Fig 18), and exhibited stereoselective recognition of monosaccharides. The monosaccharide OH groups form hydrogen bonds with the NH groups and pyridine nitrogen atom of the receptor.…”

Section: Uses Of Synthetic Dendritic Structuresmentioning

confidence: 99%

“…The dendritic branches, as well as providing the core with excellent solubility in a wide range of solvents, were found to control the enantio‐ and diastereo‐selectivity of monosaccharide complexation at the core. The strong Circular Dichroism sensory response of these hosts and their easy recyclability favours their potential as sensors of biologically important molecules 67…”

Section: Uses Of Synthetic Dendritic Structuresmentioning

confidence: 99%

See 2 more Smart Citations

Dendrimers: a review of their appeal and applications

Dykes

2001

J of Chemical Tech & Biotech

194

106

View full text Add to dashboard Cite

Dendrimer chemistry is one of the most fascinating and rapidly expanding areas of modern chemistry. This review attempts to uncover the appeal of these structurally-perfect branched macromolecules. The three intriguing regions of a dendritic molecule are discussed: the multifunctional surface, the tailored sanctuary within the branches, and the encapsulated core. The advantages of dendritic structures for property modi®cation, and their potential applications in very diverse areas are illustrated. The exciting merger of dendrimer chemistry with self-assembly offers new, stimulating avenues for exploration. Consequently, self-assembling dendrimers comprise a major section of this article.

show abstract

Section: Uses Of Synthetic Dendritic Structuresmentioning

confidence: 99%

Section: Uses Of Synthetic Dendritic Structuresmentioning

confidence: 99%

Section: Uses Of Synthetic Dendritic Structuresmentioning

confidence: 99%

See 1 more Smart Citation

Dendrimers: a review of their appeal and applications

Dykes

2001

J of Chemical Tech & Biotech

194

106

View full text Add to dashboard Cite

show abstract

“…High‐generation dendrimers with their cascade structures serve as interesting candidates for the formation of artificial macromolecular globular structures with multivalent outer shells and surfaces. Thus, there has been an immense interest in the use of dendrimers as hosts or carriers of a variety of guest molecules,1 possible molecular vehic les in drug delivery,2, 3 micelle mimics,4 polyvalent catalysts,5–9 or molecular sensors 10, 11. In the early examples of host–guest chemistry involving dendritic hosts, the substrate was bound to the interior of the dendrimer (endoreceptor), either nonspecifically12 or by well‐defined multiple hydrogen‐bonding interactions as found in the 'dendroclefts' 13.…”

Section: Introductionmentioning

confidence: 99%

New Dendrimer–Peptide Host–Guest Complexes: Towards Dendrimers as Peptide Carriers

et al. 2002

View full text Add to dashboard Cite

Adamantyl urea and adamantyl thiourea modified poly(propylene imine) dendrimers act as hosts for N-terminal tert-butoxycarbonyl (Boc)-protected peptides and form chloroform-soluble complexes. Investigations with NMR spectroscopy show that the peptide is bound to the dendrimer by ionic interactions between the dendrimer outer shell tertiary amines and the C-terminal carboxylic acid of the peptide, and also through host-urea to peptide-amide hydrogen bonding. The hydrogen-bonding nature of the peptide-dendrimer interactions was further confirmed by using Fourier transform IR spectroscopy, for which the NH- and CO-stretch signals of the peptide amide moieties shift towards lower wavenumbers upon complexation with the dendrimer. Spatial analysis of the complexes with NOESY spectroscopy generally shows close proximity of the N-terminal Boc group of the peptide to the peripheral adamantyl groups on the dendrimer host. The influence of side-chain motif on interactions with the host is analyzed by using seven different N-Boc-protected tripeptides as guests for the dendrimer. Downfield shifts of up to 1.3 ppm were observed for the guest amide NH-proton signals. These shifts decreased with increasing 'bulkiness' of the amino acid side chains. Despite this, the dendrimer was capable of making multiple peptide-dendrimer complexes when presented with a library of seven peptides. The different peptides were all present in the host, which did not show specific preferences, and could be released under mild acidic conditions. These results show the general nature of the peptide-dendrimer interactions in the formation of either single- or multiple-peptide-dendrimer complexes.

show abstract

“…Davis and coworkers (6,7) and Aoyama (8) used macrocyclic scaffolds for hydrogen-bonded saccharide complexation. Anslyn and coworkers (9-11), Inouye et al (12,13), Diederich and coworkers (14), and Mazik et al (15,16) arranged pyridine units as hydrogen-bond acceptors in complementary spatial positions as a strategy for saccharide recognition. § The detection of saccharide binding via noncovalent interactions has been attained mainly by means of 1 H-NMR spectroscopy, because most saccharides have neither a chromophore nor functional groups capable of protonation or deprotonation.…”

mentioning

confidence: 99%

Circular dichroism readout of sugar recognition in the cleft of a fused-pyridine receptor

Tamaru

Shinkai

Khasanov

et al. 2002

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

View full text Add to dashboard Cite

T he design of artificial receptors for biomimetic complexation of carbohydrates remains an important challenge of supramolecular chemistry. Sugars are generally bound in cavities or clefts of proteins via multiple hydrogen-bonding interactions involving saccharide OH groups (1-3). X-ray structures show the exclusion of most water molecules, which can otherwise hamper proteinsaccharide interaction by competing for hydrogen bonds. In efforts to bind sugars with high affinity and selectivity, chemists have attempted to mimic biotic saccharide recognition with artificial receptors, using multiple hydrogen-bonding interactions in aprotic solvents (4). The detection of saccharide binding via noncovalent interactions has been attained mainly by means of 1 H-NMR spectroscopy, because most saccharides have neither a chromophore nor functional groups capable of protonation or deprotonation. Thus, it is very difficult or nearly impossible to design convenient saccharide-sensing systems. To the best of our knowledge, there are only a few examples in which circular dichroism (CD) or fluorescence spectroscopic methods, which are more expeditious for developing practical saccharide-sensing systems, have been adopted (12,(18)(19)(20).Several fused-pyridine receptors have been developed for recognition of creatinine, guanidinium, urea, and related molecules (refs. 21-24 and references in refs. 23 and 24). Among them, host 1 (Fig. 1) has two carboxylate anions and four basic nitrogens capable of forming both ionic and neutral hydrogenbonding interactions, making 1 an effective host for guanidines (e.g., arginine) in water (24). As discussed (25), the naphthyridine moiety and adjacent pyridine rings of 1 are twisted with respect to each other to avoid an energetically unfavorable eclipsed conformation in the CH 2 CH 2 linkages, and the cleft composed of four basic nitrogens is comparable in size to a monosaccharide (Fig. 1). We found consequently that 1 binds cationic monosaccharides with high affinity in methanol and that the binding event could be monitored by induced CD (ICD) arising from the twisting direction of the naphthyridine-pyridine NCCN torsional angle (25). We reasoned that a neutral analog of 1 might bind neutral saccharides in a less polar solvent and that complexation could be detected by ICD, as well as by fluorescence spectroscopy. We converted 1 to diamide 2 and now found that both CD and fluorescence spectra were sensitive to the binding of saccharides 3-9 (Scheme 1). (For methods used to obtain saccharide guests and to calculate association constants, see supporting information, which is published on the PNAS web site, www.pnas.org.) In particular, the CD sign clearly reflects the absolute configuration of the saccharide guest.The absorption spectra of diamide 2 in CHCl 3 obeyed the Lambert-Beer law over concentrations of 0 to 1.0 ϫ 10 Ϫ4 M. This result implies that 2 does not aggregate in CHCl 3 in this concentration range. As shown in Fig. 2, an ICD band and an excitoncoupling-type band (25) appear at 31...

show abstract

Dendroclefts: Optically Active Dendritic Receptors for the Selective Recognition and Chiroptical Sensing of Monosaccharide Guests

Cited by 69 publications

References 13 publications

Dendrimers: a review of their appeal and applications

Dendrimers: a review of their appeal and applications

New Dendrimer–Peptide Host–Guest Complexes: Towards Dendrimers as Peptide Carriers

Circular dichroism readout of sugar recognition in the cleft of a fused-pyridine receptor

Contact Info

Product

Resources

About