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Lipid bilayer environments control exchange kinetics of deep cavitand hosts and enhance disfavored guest conformations.

ABSTRACT: The effects on the molecular recognition properties of water-soluble deep cavitand hosts upon embedding them in phosphocholine lipid bilayer environments have been studied by 2D NMR experiments. By employing suitable guests containing 19F or 13C nuclei that can be encapsulated inside the host, 2D EXSY NMR experiments can be used to analyze and compare the in/out guest exchange rates in aqueous solution, isotropically tumbling micelles, or magnetically ordered bicelles. These analyses show that embedding the deep cavitands in lipid bilayers slows the guest exchange rate, due to the lipids acting as a "compression sleeve" around the host, restricting guest egress. This effect also enhances guest conformations in the host that are not observed in free solution, such as axial cyclohexane conformers and ketone hydrates.

SUBMITTER: Perez L

PROVIDER: S-EPMC5890788 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Environment-dependent guest exchange in supramolecular hosts.

Project description:Dynamic exchange of guest molecules, encapsulated in host assemblies, is a phenomenon in supramolecular chemistry that has important implications in several applications. While the mechanism of exchange in micellar assemblies has been previously investigated, the effect of host and guest environment upon the guest-exchange dynamics has received little attention, if any. In this paper, we study the guest-exchange mechanism in pH-sensitive nanogels along with pH-insensitive nanogels as a control. By systematically comparing the behavior of these nanogels, we show that size, concentration, and hydrophobicity can all play a critical role in guest-exchange dynamics. More importantly, these studies reveal that the dominant mechanism of guest exchange can intimately depend on environmental factors.

| S-EPMC4204928 | biostudies-literature

Selective protein recognition in supported lipid bilayer arrays by tailored, dual-mode deep cavitand hosts.

Project description:Self-folding deep cavitands with variably functionalized upper rims are able to selectively immobilize proteins at a biomimetic supported lipid bilayer surface. The immobilization process takes advantage of the dual-mode binding capabilities of the hosts, combining a defined binding pocket with upper rim charged/H-bonding groups. A variety of proteins can be selectively immobilized at the bilayer interface, either via complementary charge/H-bonding interactions, cavity-based molecular recognition, or a combination of both. The immobilization process can be used to bind unmodified native proteins, epitopes for bioadhesion, or proteins covalently modified with suitable RNMe3+ binding "handles" and charged groups that can either match or mismatch with the cavitand rim. The immobilization process can be monitored in real time using surface plasmon resonance (SPR) spectroscopy, and applied to the construction of cavitand:lipid arrays using the hosts and trehalose vitrified phospholipid vesicles. The selective, dual-mode protein recognition is maintained in the arrays, and can be visualized using SPR imaging.

| S-EPMC6041475 | biostudies-literature

A light controlled cavitand wall regulates guest binding.

Project description:Here we report a cavitand with a photochemical switch as one of the container walls. The azo-arene switch undergoes photoisomerization when subjected to UV light producing a self-fulfilled cavitand. This process is thermally and photochemically reversible. The reported cavitand binds small molecules and these guests can be ejected from the cavitand through this photochemical process.

| S-EPMC3010387 | biostudies-literature

Guest recognition in a partially bridged deep cavitand.

Project description:The synthesis of a new deep cavitand partially bridged via disulfide bonds is described. Its thermodynamic and kinetic complexation parameters are compared with those of an unbridged analogue. The disulfide bridges cause deviations in ?H and ?S but result in only small differences in ?G of complexation. The bridges increase the activation barrier for guest dissociation and lead to complexes with enhanced kinetic stability.

| S-EPMC2966534 | biostudies-literature

Ternary host-guest complexes with rapid exchange kinetics and photoswitchable fluorescence.

Project description:Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems-and ultimately materials-whose desired properties could be tailored "on demand" rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.

| S-EPMC9473544 | biostudies-literature

Sensing of citrulline modifications in histone peptides by deep cavitand hosts.

Project description:Arrayed cavitand:fluorophore sensor complexes can selectively sense small citrulline modifications at arginine residues on post-translationally modified peptides. The sensor can differentiate between different numbers of citrulline modifications, and a simple two-fluorophore, 6-component array can effect cross-reactive discrimination between single modifications in aqueous solution.

| S-EPMC6872487 | biostudies-literature

Guest/Host Complexes of Octa Acid and Amphiphilic Benzylidene-3-methylimidazolidinones Exchange Hosts within the NMR Time Scale.

Project description:Cavitand octa acid (OA) is established to form a stable capsular assembly with one or two hydrophobic guest molecules (1:2 or 2:2 guest/host complex). Examples are known in which the guest molecule tumbles within the capsule without disrupting the structure of the capsuleplex. This process makes the two OA molecules that form the capsule magnetically equivalent. In this study, we have examined the dynamics of capsules that host amphiphilic benzylidene-3-methylimidazolidinone molecules as guests. In these capsuleplexes, although the guest does not tumble, the two OA molecules become magnetically equivalent because the two OA molecules that form the capsule exchange their positions in the NMR time scale. This is equivalent to the content of the capsule remaining stationary while the capsule swirls around it. Benzylidene-3-methylimidazolidinones form both 1:1 and 1:2 supramolecular complexes with cavitand OA. Two-dimensional NMR, ROESY, and NOESY data suggest that in a 300 ms time scale, the two halves of the capsule exchange between themselves and with free OA. The conclusion drawn here provides valuable information concerning the stability of the OA capsuleplex and cavitandplex that is used as the well-defined space to control the excited-state chemistry and dynamics of confined guest molecules.

| S-EPMC7161058 | biostudies-literature

Crystal structure of a host-guest complex between mephedrone hydro-chloride and a tetra-phospho-nate cavitand.

Project description:A new supra-molecular complex (I) between the tetra-phospho-nate cavitand Tiiii[C3H7,CH3,C6H5] [systematic name: 2,8,14,20-tetra-propyl-5,11,17,23-tetra-methyl-6,10:12,16:18,22:24,4-tetra-kis-(phenyl-phospho-nato-O,O')resorcin[4]arene] and mephedrone hydro-choride {C11H16NO+·Cl-; systematic name: meth-yl[1-(4-methyl-phen-yl)-1-oxopropan-2-yl]aza-nium chloride} has been obtained and characterized both in solution and in the solid state. The complex of general formula (C11H16NO)@Tiiii[C3H7,CH3,C6H5]Cl·CH3OH or C11H16NO+·Cl-·C68H68O12P4·CH3OH, crystallizes in the monoclinic space group P21/c with one lattice methanol mol-ecule per cavitand, disordered over two positions with occupancy factors of 0.665?(6) and 0.335?(6). The mephedrone guest inter-acts with the P=O groups at the upper rim of the cavitand through two charge-assisted N-H?O hydrogen bonds, while the methyl group directly bound to the amino moiety is stabilized inside the ? basic cavity via cation?? inter-actions. The chloride counter-anion is located between the alkyl legs of the cavitand, forming C-H?Cl inter-actions with the aromatic and methyl-enic H atoms of the lower rim. The chloride anion is also responsible for the formation of a supra-molecular chain along the b-axis direction through C-H?Cl inter-actions involving the phenyl substituent of one phospho-nate group. C-H?O and C-H?? inter-actions between the guest and adjacent cavitands contribute to the formation of the crystal structure.

| S-EPMC6362660 | biostudies-literature

Host-guest supra-molecular inter-actions between a resorcinarene-based cavitand bearing a -COOH moiety and acetic acid.

Project description:The cavitand 5,11,17,23-tetra-methyl-4,24:6,10:12,16:18,22-tetra-kis-(methyl-enedi-oxy)resorcin[4]arene functionalized at the upper rim with a carb-oxy-lic acid group, CavCOOH-in, of chemical formula C37H32O10, was synthesized in order to study its supra-molecular inter-actions with acetic acid in the solid state. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a di-chloro-methane-acetone solution of CavCOOH-in, to which glacial acetic acid had been added. The resulting compound, C37H32O10·2C2H4O2 (1) crystallizes in the space group P and its asymmetric unit consists of one mol-ecule of cavitand and two mol-ecules of acetic acid, one of which is encapsulated inside the aromatic cavity and disordered over two positions with a refined occupancy ratio of 0.344?(4):0.656?(4). The guest inter-acts with the host primarily through its methyl group, which (in both orientations) forms C-H?? inter-actions with the benzene rings of the cavitand. The crystal structure of 1 is dominated by O-H?O and C-H?O hydrogen bonding due to the presence of acetic acid and of the carb-oxy-lic group functionalizing the upper rim. Further stabilization is provided by offset ?-? stacking inter-actions between the aromatic walls of adjacent cavitands [inter-centroid distance = 3.573?(1)?Å].

| S-EPMC6399691 | biostudies-literature

Cell and Protein Recognition at a Supported Bilayer Interface via In Situ Cavitand-Mediated Functional Polymer Growth.

Project description:Water-soluble deep cavitands embedded in a supported lipid bilayer are capable of anchoring ATRP initiator molecules for the in situ synthesis of primary amine-containing polymethacrylate patches at the water:membrane interface. These polymers can be derivatized in situ to incorporate fluorescent reporters, allow selective protein recognition, and can be applied to the immobilization of nonadherent cells at the bilayer interface.

| S-EPMC4706080 | biostudies-literature

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