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Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis.

ABSTRACT: Chiral macromolecules have been widely used as synthetic pockets to mimic natural enzymes and promote asymmetric reactions. An achiral host, cucurbit[8]uril (CB[8]), was used for an asymmetric Lewis acid catalyzed Diels-Alder reaction. We achieved a remarkable increase in enantioselectivity and a large rate acceleration in the presence of the nanoreactor by using an amino acid as the chiral source. Mechanistic and computational studies revealed that both the amino acid-Cu(2+) complex and the dienophile substrate are included inside the macrocyclic host cavity, suggesting that contiguity and conformational constraints are fundamental to the catalytic process and rate enhancement. These results pave the way towards new studies on asymmetric reactions catalyzed in confined achiral cavities.

SUBMITTER: Zheng L

PROVIDER: S-EPMC4643185 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature

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Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis.

Zheng Lifei L Sonzini Silvia S Ambarwati Masyitha M Rosta Edina E Scherman Oren A OA Herrmann Andreas A

Angewandte Chemie (International ed. in English) 20150907 44

Chiral macromolecules have been widely used as synthetic pockets to mimic natural enzymes and promote asymmetric reactions. An achiral host, cucurbit[8]uril (CB[8]), was used for an asymmetric Lewis acid catalyzed Diels-Alder reaction. We achieved a remarkable increase in enantioselectivity and a large rate acceleration in the presence of the nanoreactor by using an amino acid as the chiral source. Mechanistic and computational studies revealed that both the amino acid-Cu(2+) complex and the die ...[more]

PMID: 26383272

Similar Datasets

Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis.

Project description:Chiral macromolecules have been widely used as synthetic pockets to mimic natural enzymes and promote asymmetric reactions. An achiral host, cucurbit[8]uril (CB[8]), was used for an asymmetric Lewis acid catalyzed Diels-Alder reaction. We achieved a remarkable increase in enantioselectivity and a large rate acceleration in the presence of the nanoreactor by using an amino acid as the chiral source. Mechanistic and computational studies revealed that both the amino acid-Cu2+ complex and the dienophile substrate are included inside the macrocyclic host cavity, suggesting that contiguity and conformational constraints are fundamental to the catalytic process and rate enhancement. These results pave the way towards new studies on asymmetric reactions catalyzed in confined achiral cavities.

| S-EPMC4955226 | biostudies-literature

Supramolecular Complexation of Azobenzene Dyes by Cucurbit[7]uril.

Project description:This report describes cucurbit[7]uril (CB7) complexation of azobenzene dyes that have a 4-(N,N'-dimethylamino) or 4-amino substituent. Absorption and NMR data show that CB7 encapsulates the protonated form of the azobenzene and that the complexed dye exists as its azonium tautomer with a trans azo conformation and substantial quinoid resonance character. Because CB7 complexation stabilizes the dye conjugate acid, there is an upward shift in its pKa, and in one specific case, the pKa of the protonated azobenzene is increased from 3.09 to 4.47. Molecular modeling indicates that the CB7/azobenzene complex is stabilized by three major noncovalent factors: (i) ion-dipole interactions between the partially cationic 4-(N,N'-dimethylamino) or 4-amino group on the encapsulated protonated azobenzene and the electronegative carbonyl oxygens on CB7, (ii) inclusion of the upper aryl ring of the azobenzene within the hydrophobic CB7 cavity, and (iii) a hydrogen bond between the proton on the azo nitrogen and CB7 carbonyls. CB7 complexation enhances azobenzene stability and increases azobenzene hydrophilicity; thus, it is a promising way to improve azobenzene performance as a pigment or prodrug. In addition, the striking yellow/pink color change that accompanies CB7 complexation can be exploited to create azobenzene dye displacement assays with naked eye detection.

| S-EPMC10843849 | biostudies-literature

Supramolecular Encapsulation of a Neurotransmitter Serotonin by Cucurbit[7]uril.

Project description:pH-dependent host-guest complexation of a monoamine neurotransmitter, Serotonin, with cucurbit[7]uril has been thoroughly investigated. The binding phenomena were explored using steady-state and time-resolved fluorescence spectroscopy at different pH values. At lower pH, i.e., protonated Serotonin, the binding affinity with cucurbit[7]uril was significantly higher compared to higher pH. Furthermore, detailed NMR titration experiments depicted the solution structure of the host-guest complex through the complexation induced chemical shift values. A competitive binding assay with cesium ions at pD 2.8 was subsequently performed for the further manifestation of the binding. Finally, the molecular docking studies provided well-documented proof of the 1:1 inclusion complex and the geometry of the complex. We believe that understanding from such studies can be important for pH-controlled delivery of serotonin for biological applications.

| S-EPMC7645158 | biostudies-literature

4-Sulfocalix[4]arene/Cucurbit[7]uril-Based Supramolecular Assemblies through the Outer Surface Interactions of Cucurbit[<i>n</i>]uril.

Project description:Upon mixing of aqueous solutions of the freely soluble building blocks cucurbit[7]uril (Q[7]) and 4-sulfocalix[4]arene (SC[4]A), white microcrystals instantly separate in near-quantitative yield. The driving force for this assembly is suggested to be the outer-surface interaction of the Q[n]. Dynamic light scattering, scanning electron microscopy, and NMR (diffusion-ordered NMR spectroscopy) analyses have confirmed the supramolecular aggregation of Q[7] and SC[4]A. Titration 1H NMR spectroscopy and isothermal titration calorimetry have shown that the interaction ratio of Q[7] and SC[4]A is close to 3:1. Moreover, the Q[7]/SC[4]A-based supramolecular assembly can accommodate molecules of some volatile compounds or luminescent dyes. Thus, this work offers a simple and highly efficient means of preparing adsorbent or solid fluorescent materials.

| S-EPMC6644559 | biostudies-literature

Injectable Cucurbit[8]uril-Based Supramolecular Gelatin Hydrogels for Cell Encapsulation.

Project description:Recent efforts to develop hydrogel biomaterials have focused on better recapitulating the dynamic properties of the native extracellular matrix. In hydrogel biomaterials, binding thermodynamics and cross-link kinetics directly affect numerous bulk dynamic properties such as strength, stress relaxation, and material clearance. However, despite the broad range of bulk dynamic properties observed in biological tissues, present strategies to incorporate dynamic linkages in cell-encapsulating hydrogels rely on a relatively small number of dynamic covalent chemical reactions and host-guest interactions. To expand this toolkit, we report the preparation of supramolecular gelatin hydrogels with cucurbit[8]uril (CB[8])-based cross-links that form on demand via thiol-ene reactions between preassembled CB[8]·FGGC peptide ternary complexes and grafted norbornenes. Human fibroblast cells encapsulated within these optically transparent, shear thinning, injectable hydrogels remained highly viable and exhibited a well-spread morphology in culture. These CB[8]-based gelatin hydrogels are anticipated to be useful in applications ranging from bioprinting to cell and drug delivery.

| S-EPMC7286610 | biostudies-literature

Supramolecular Crystal Networks Constructed from Cucurbit[8]uril with Two Naphthyl Groups

Project description:Naphthyl groups are widely used as building blocks for the self-assembly of supramolecular crystal networks. Host–guest complexation of cucurbit[8]uril (Q[8]) with two guests NapA and Nap1 in both aqueous solution and solid state has been fully investigated. Experimental data indicated that double guests resided within the cavity of Q[8], generating highly stable homoternary complexes NapA2@Q[8] and Nap12@Q[8]. Meanwhile, the strong hydrogen-bonding and π···π interaction play critical roles in the formation of 1D supramolecular chain, as well as 2D and 3D networks in solid state.

| S-EPMC9822147 | biostudies-literature

Cucurbit[10]uril.

Project description:Melamine diamine 1 is able to displace CB[5] from the CB[10].CB[5] complex resulting in CB[10].12 and precipitated CB[5].1. We were able to isolate free CB[10] by treatment of CB[10].1 with acetic anhydride followed by washing with MeOH, DMSO, and water. The spacious cavity of CB[10] is able to complex large guests, including a cationic calix[4]arene derivative in its 1,3-alternate form (CB[10].1,3-alt-3). The addition of adamantane carboxylic acid (4) to CB[10].3 triggers a conformational change during the formation of termolecular complex CB[10].cone-3.4.

| S-EPMC2538447 | biostudies-literature

Interaction of Phenyl-Substituted Diazaperylenium with Cucurbit[n]uril: Complex versus Supramolecular Polymer.

Project description:A phenyl-substituted diazaperylenediium dication (DAP) was synthesized that shows concentration-dependent aggregation in water. The host-guest complexation of DAP was studied with the macrocyclic host cucurbit[n]uril (n = 7, 8) in water. With CB[7], it forms a 1:2 complex by placing two aryl substituents inside the CB[7]; whereas, with CB[8], a supramolecular polymer is formed. The resulting complex and supramolecular polymer have been characterized by ITC (isothermal titration calorimetry), ESI-MS (electrospray ionization mass spectrometry), 1H NMR (proton nuclear magnetic resonance), 2D NOESY (two-dimensional nuclear Overhauser enhancement spectroscopy), and DOSY (diffusion-ordered spectroscopy) spectra.

| S-EPMC7081634 | biostudies-literature

Supramolecular Controlled Cargo Release via Near Infrared Tunable Cucurbit[7]uril-Gold Nanostars.

Project description:The near infrared (NIR) absorption and average particle size of gold nanostars (GNSs) can be precisely controlled by varying the molar ratios of cucurbit[7]urils (CB[7]) and GNSs in aqueous solution. GNSs modified with CB[7] achieved high cargo loading with thermally activated release upon the NIR laser irradiation.

| S-EPMC4768098 | biostudies-literature

Supramolecular Fluorescence Probe Based on Twisted Cucurbit[14]uril for Sensing Fungicide Flusilazole.

Project description:The host-guest complex of the common dye, thioflavin T (ThT), and twisted cucurbit[14]uril (tQ[14]) was selected as a fluorescent probe to determine non-fluorescent triazole fungicides, including flusilazole, azaconazole, triadimefon, tebuconazole, tricyclazole, flutriafol, penconazole, and triadimenol isomer A, in an aqueous solution. The experimental results reveal that the ThT@tQ[14] probe selectively responded to flusilazole with significant fluorescence quenching and a detection limit of 1.27 × 10-8 mol/L. In addition, the response mechanism involves not only a cooperation interaction-ThT occupies a side-cavity of the tQ[14] host and the triazole fungicide occupies another side-cavity of the tQ[14] host-but also a competition interaction in which both ThT and the triazole fungicide occupy the side-cavities of the tQ[14] host.

| S-EPMC6437033 | biostudies-literature

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