Molecular loop lock: a redox-driven molecular machine based on a host-stabilized charge-transfer complex.
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Biomedical subjects
Publications and source records attributed to Kimoon Kim.
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Novel artificial ion channels (1 and 2) based on CB[n] (n = 6 and 5, respectively) synthetic receptors with carbonyl-fringed portals (diameter 3.9 and 2.4 A, respectively) can transport proton and alkali metal ions across a lipid membrane with ion selectivity. Fluorometric experiments using large unilamellar vesicles showed that 1 mediates proton transport across the membranes, which can be blocked by a neurotransmitter, acetylcholine, reminiscent of the blocking of the K+ channels by polyamines. The alkali metal ion transport activity of 1 follows the order of Li+ > Cs+ approximately Rb+ > K+ > Na+, which is opposite to the binding affinity of CB[6] toward alkali metal ions. On the other hand, the transport activity of 2 follows the order of Li+ > Na+, which is also opposite to the binding affinity of 2 toward these metal ions, but virtually no transport was observed for K+, Rb+, and Cs+. It is presumably because the carbonyl-fringed portal size of 2 (diameter 2.4 A) is smaller than the diameters of these alkali metal ions. To determine the transport mechanism, voltage-clamp experiments on planar bilayer lipid membranes were carried out. The experiments showed that a single-channel current of 1 for Cs+ transport is approximately 5 pA, which corresponds to an ion flux of approximately 3 x 107 ions/s. These results are consistent with an ion channel mechanism. Not only the structural resemblance to the selectivity filter of K+ channels but also the remarkable ion selectivity makes this model system unique.
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A new 3D metal-organic framework with a (3,4)-connected network topology is synthesized from an ionic liquid medium; its highly symmetrical structure comprises doubly interpenetrating nets with the cubic-C3N4 topology.
This paper describes the synthesis of a tri(ethylene oxide)-attached fourth-generation poly(amidoamine) dendrimer (EO3-dendrimer) and the characterization of its layers on gold. NMR analysis and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed that about 61 amine groups of a G4 PAMAM dendrimer were covalently conjugated with tri(ethylene oxide) units, accounting for a 95% modification level. Layers of the EO3-dendrimer were formed on gold, and the resulting surface was characterized by infrared reflection absorption spectroscopy, ellipsometry, and contact angle goniometry. The EO3-dendrimer resulted in more hydrophilic and less compact layers with no substantial deformation of the molecule during layer formation by virtue of the EO3 units, compared to a PAMAM dendrimer. Interestingly, the specific binding of avidin to the biotinylated layers of the EO3-dendrimer approached a surface density of 5.2 +/- 0.2 ngmm-2, showing about 92% of full surface coverage. The layers of the EO3-dendrimer were found to be more resistant to nonspecific adsorption of proteins than PAMAM dendrimer layers when bovine serum albumin and serum proteins were tested.
A novel approach to the noncovalent synthesis of molecular necklaces successfully led to the first quantitative self-assembly of a molecular necklace [6]MN, in which five small rings are threaded on a large ring, from 10 components. Our strategy involves the host-guest complex formation between the molecular host cucurbit[8]uril (CB[8]) and a guest molecule in which an electron donor and an electron acceptor unit are connected by a rigid linker with a proper angle, to form a cyclic oligomer through the host-stabilized intermolecular charge-transfer (CT) complex formation. In the structure of the molecular necklace [6]MN, five molecules of the guest form a cyclic framework by the intermolecular CT interactions, on which five CB[8] molecules are threaded with an arrangement reminiscent of a five-fold propeller. The molecular necklace measures approximately 3.7 nm in diameter and approximately 1.8 nm in thickness.
The first stable pi-dimer of a tetrathiafulvalene (TTF) cation radical encapsulated in the cavity of cucurbit[8]uril has been isolated at room temperature and fully characterized; it shows absorption bands at 400, 540 and 760 nm, characteristic of the TTF cation radical dimer.
A novel supramolecular polymer (poly(pseudorotaxane)) in which the repeating units are linked by host-stabilized charge-transfer interaction between the guest molecules is grown on gold and characterized.
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Novel microporous metal-organic framework material composed of Mn(II) and formate ions displays permanent porosity, high thermal stability, and size-selective gas sorption behavior. The framework is stable enough to maintain single crystallinity after the complete guest removal at 150 degrees C under a reduced pressure. Most importantly, it selectively adsorbs H2 and CO2 but not N2 and other gases with larger kinetic diameters, which appears to be due to the small aperture of the channels. Despite a moderate H2 storage capacity, which is however still higher than that of any zeolite, its H2 surface coverage is one of the highest among the known microporous materials. Thus this new zeolite-like material made of a simple organic building block may find useful applications in gas separation and sensor.
cis-Diaminostilbene dihydrochloride encapsulated in cucurbit[7]uril does not spontaneously isomerize to the trans isomer at room temperature as a result of the strong host-guest interactions including strong hydrogen bonds between the two protonated amine termini of the C-shaped guest and the portal oxygen atoms of the host.
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A long-standing problem in cucurbituril chemistry is answered through the first direct functionalization of cucurbit[n]uril (CB[n]; n = 5-8)) leading to perhydroxyCB[n] which can be further modified to provide tailored CB[n] derivatives with desired functional groups and good solubility. Anchoring a CB[6] derivative on the surface and its potential application as a sensor are demonstrated. A CB[6] derivative forms nanospheres with possible use in protein and peptide drug delivery.
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The supramolecular chemistry of cucurbituril, a synthetic receptor, is fascinating because of the remarkable guest binding behavior of the host. Studies in the field, however, have met with limitations, since the only species known was the hexameric macrocyclic compound, cucurbit[6]uril. Recently we synthesized its homologues, cucurbit[n]uril (n = 5, 7, 8), and derivatives. These new members of the cucurbituril family have expanded the scope further, and interest in them has grown enormously. This Account is a compilation of recent literature covering the syntheses of the homologues and derivatives, and their supramolecular chemistry.
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For the first time, host-induced intramolecular charge-transfer complex formation in a guest containing both an electron donor and an electron acceptor is demonstrated in the cucurbit[8]uril cavity, leading to unusual back-folding of the guest molecule.
The binding stoichiometry of a host-guest complex can be effectively controlled by the redox chemistry of the guest: a 1:1 inclusion complex of methylviologen dication (MV2+) in cucurbit[8]uril (CB[8]) converts completely and reversibly to a 2:1 inclusion complex of cation radical (MV+.) in CB[8] upon the reduction of the guest.