We herein describe the preparation, characterization, and recognition characteristics of novel hexapodal capsule 1 composed of two benzenes joined by six hydrogen bonding (HB) groups to encircle space. This barrel-shaped host was obtained by reversible imine condensation of hexakis-aldehyde 2 and hexakis-amine 3 in the presence of oxyanions or halides acting as templates. Fascinatingly, capsule 1 includes 18 HB donating (Csp2–H and N–H) and 12 HB accepting groups (CO and CN) surrounding a binding pocket (78 Å3). In this regard, the complexation of fluoride, chloride, carbonate, sulfate, and hydrogen phosphate was probed by NMR spectroscopy (DMSO) and X-ray diffraction analysis to disclose the adaptive nature of 1 undergoing an adjustment of its conformation to complement each anionic guest. Furthermore, the rate by which encapsulated chloride was substituted by sulfate or hydrogen phosphate was slow (>7 days) while the stability of [SO4⊂1]2– was greatest in the series with K a > 107 M–1 in highly competitive DMSO. With facile access to 1, the stage is set to probe this modular, polyvalent, and novel host to further improve the extraction of tetrahedral oxyanions from waste and the environment or control their chemistry in living systems.
Living systems use chemical fuels to transiently assemble functional structures. As a step toward constructing abiotic mimics of such structures, we herein describe dissipative formation of covalent basket cage CBC 5 by reversible imine condensation of cup‐shaped aldehyde 2 (i.e., basket) with trivalent aromatic amine 4. This nanosized [4+4] cage (V=5 nm3, Mw=6150 Da) has shape of a truncated tetrahedron with four baskets at its vertices and four aromatic amines forming the faces. Importantly, tris‐aldehyde basket 2 and aliphatic tris‐amine 7 undergo condensation to give small [1+1] cage 6. The imine metathesis of 6 and aromatic tris‐amine 4 into CBC 5 was optimized to bias the equilibrium favouring 6. Addition of tribromoacetic acid (TBA) as a chemical fuel perturbs this equilibrium to result in the transient formation of CBC 5, with subsequent consumption of TBA via decarboxylation driving the system back to the starting state.
Supramolecular hosts bind to inorganic anions at a fast rate and select them in proportion with thermodynamic stability of the corresponding [anion�host] complexes, forming in a reversible manner. In this study, we describe the action of hexapodal capsule 1 and its remarkable ability to select anions based on a large span of rates by which they enter this host. The thermodynamic affinity of 1 toward eighteen anions extends over eight orders of magnitude (0 < K a < 10 8 M À 1 ; 1 H NMR spectroscopy). The capsule would retain CO 3 2À (K a = 10 7 M À 1 ) for hours in the presence of eleven competing anions, including stronger binding SO 4 2À , HAsO 4 2À and HPO 4 2À (K a = 10 7 -10 8 M À 1 ). The observed selection resulted from 1 possessing narrow apertures (ca. 3 × 6 Å) comparable in size to anions (d = 3.5-7.1 Å) slowing down the encapsulation to last from seconds to days. The unorthodox mode of action of 1 sets the stage for creating hosts that pick anions by their ability to access the host.
We describe a preparative method for directing Mizoroki-Heck cyclotrimerization of enantioenriched bromonorbornenes into molecular baskets having increasingly deeper and extendable aromatic cavities. Such diastereoselective cyclotrimerizations of the bromo-olefinic substrates resulted...
Nerve agents are tetrahedral organophosphorus compounds (OPs) that were developed in the last century to irreversibly inhibit acetylcholinesterase (AChE) and therefore impede neurological signaling in living organisms. Exposure to OPs leads to a rapid development of symptoms from excessive salivation, nasal congestion and chest pain to convulsion and asphyxiation which if left untreated may lead to death. These potent toxins are prepared on a large scale from inexpensive staring materials, making it feasible for terrorist groups or states to use them against military and civilians. The existing antidotes provide limited protection and are difficult to apply to a large number of affected individuals. While new prophylactics are currently being developed, there is still need for therapeutics capable of both preventing and reversing the effects of OP poisoning. In this review, we describe how the science of molecular recognition can expand the pallet of tools for rapid and safe sequestration of nerve agents.
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