This thesis deals with multivalent ß-cyclodextrin (CD) host-guest interactions in solution and at interfaces

Mulder, Alart

English

This thesis deals with multivalent β-cyclodextrin (CD) host-guest interactions in solution and at interfaces. In solution, multivalency has been exploited to develop strongly binding CD dimers. Switchable tethers have been implemented to control the possible relative orientations of the two CD cavities of the CD dimers and therewith the extent of multivalency in the binding of guest molecules, giving access to tunable receptor molecules, the binding properties of which can be controlled by external stimuli

University of Twente Research Information

Multivalent cyclodextrin receptors in solution and at surfaces

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(s, 24H, NHCCH2), 1.78 (m, 12H, NCH2CH2CH2N), 1.58 (s, 24H, CHCH2CH), 1.40-1.21 (m, 8H, 164 Multivalent interactions at CD monolayers on silicon oxide NCH2CH2CH2CH2CH2CH2); 13C NMR (CDCl3): δ 158.7,

(s, 6H); 13C NMR (D2O, ref. CH3OD): δ 166.8,

100 For comprehensive reviews on guest complexation by cyclodextrins see: a

102, 9820-9824. 4 Quenching especially hampers fluorescence spectroscopy at continuous metallic films, but is less predominant at metallic nanoparticles or islands, see for example ref. 2 and: a

11 For experimental details see:

121, 67. For a more recent review see: Alfimov,

123, 12488-12494. 4 For metal-switchable CD dimers see: a

14 This reaction was performed at low temperature to assure the formation of wellordered monolayers: a

1H NMR (CD3OD): δ 7.78 (dd,

1H NMR (CDCl3): δ 5.06 (d,

3 For photoswitchable CD dimers see: a

30 It has been shown that typically more than a monolayer is transferred during µCP:

4553-4560, and references cited therein.

48 General review on glycoproteins:

5 For CDs capped with photoswitchable moieties see: a

5-8 Cyclodextrin dimers are able to * Parts of this work have been published in:

6 For photoswitchable crown ethers see: a

7 For recent examples of photoswitchable receptors based on other host molecules see: a

7 For streptavidin and biotin: Ka ≈ 10 15 M -1; -21 kcal mol -1

7 The number of functional groups that can be directly introduced onto SiO2 substrates is very limited, see:

8 For an extensive review on binding affinities and the comparison of cyclodextringuest interactions with biomolecular interactions see:

8 For recent examples of metal-switchable receptors based on other host molecules see: a

9 a) Special Issue “Cyclodextrins”:

A general model for multivalent binding on surfaces will be presented: Huskens,

Actuators B

AFM experiments were performed by Tommaso Auletta and Barbara Dordi. For experimental details see: a

Alart Mulder werd geboren op 15

An Introduction to Ultrathin Organic Films,

Colloid Interface Sci.

Controlled Release

Drug Discovery Today

Faraday Trans.

For an intramolecular n-valent interaction with an association constant Kn, the effective molarity (EM) is given by Equation 1.

For comparison, the closed form of the dithienylethene-tethered dimer was found to bind TSPP with an enthalpy of binding only slightly higher (1 kcal mol -1) than the binding enthalpy for the complexation of TSPP by native CD (see Chapter 3).

For the concept of EM applied to reaction kinetics see for example: a

For the concept of EM applied to self-assembly in solution see for example: Ercolani,

For two independent, sequential binding events this implies:

Inclusion Phenom. Macrocyclic Chem.

Macrocyclic Chem.

Molecular Switches,

MS (MALDI-TOF): m/z calcd for [M+H] + 1268.0, found 1268.6. Amino-tetraadamantylurea wedge 9. To a cooled solution of

MS (MALDI-TOF): m/z calcd for [M+H] + 1300.6; found 1300.4. Substrate preparation. Four-inch polished, 100-cut, p-doped silicon wafers, cut into 2

Multivalency and its role in cyclodextrin systems 45 52 Particularly well-characterized aggregating systems can be found in: a) Olsen,

o i o o

other p-substituted phenylenes have been used previously as linking groups at SAMs:

Principles of Polymer Chemistry, Cornell Univ.

Purification of Laboratory Chemicals,

Rapid Commun.

Red Al is a trade name for solutions of sodium bis(2-methoxyethoxy)aluminum dihydride in toluene.

Science

SHELSX-86 Program for crystal structure determination,

SHELSX-97 Program for crystal structure refinement,

Spectrochimica Acta A,

Stereochemistry of Carbohydrates,

Tetrahedron Asymmetry

The channels are situated at a protein surface and therefore the probing volume of the uncomplexed guest site is constituted of half a sphere (2πr 3/3).

The synthesis of this compound is described in Chapter 3.

Thesis,

This concept has also been applied successfully to the pentavalent binding to toxins.

Typical data obtained with a 5 mM aqueous solution of dimer 4 in an NMR tube, irradiated at 313 nm for 2.5 h: 1H NMR spectroscopy: 34 % open form and 66 % closed form; UV-vis spectroscopy and modeling: 33 % open form, 67 % closed form.

Virology

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Multivalent cyclodextrin receptors in solution and at surfaces

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