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The diverse coordination modes and electronic features of actinide complexes of porphyrins and related oligopyrrolic systems (referred to as "porpyrinoids") have been the subject of interest since the 1960s. Given their stability and accessibility, most work with actinides has focused on thorium and uranium. This trend is also seen in the case of porphyrinoid-based complexation studies. Nevertheless, the diversity of ligand environments provided by porphyrinoids has led to the stabilization of a number of unique complexes with the early actinides that are often without structural parallel within the broader coordination chemical lexicon. This review summarizes key examples of prophyrinoid actinide complexes reported to date, including the limited number of porphyrinoid systems involving transuranic elements. The emphasis will be on synthesis and structure; however, the electronic features and reactivity pattern of representative systems will be detailed as well. Coverage is through December of 2021.
Assuntos
Elementos da Série Actinoide , Porfirinas , Urânio , Ligantes , Porfirinas/química , Tório/química , Urânio/químicaRESUMO
Cation and anion recognition have both played central roles in the development of supramolecular chemistry. Much of the associated research has focused on the development of receptors for individual cations or anions, as well as their applications in different areas. Rarely is complexation of the counterions considered. In contrast, ion pair recognition chemistry, emerging from cation and anion coordination chemistry, is a specific research field where co-complexation of both anions and cations, so-called ion pairs, is the center of focus. Systems used for the purpose, known as ion pair receptors, are typically di- or polytopic hosts that contain recognition sites for both cations and anions and which permit the concurrent binding of multiple ions. The field of ion pair recognition has blossomed during the past decades. Several smaller reviews on the topic were published roughly 5 years ago. They provided a summary of synthetic progress and detailed the various limiting ion recognition modes displayed by both acyclic and macrocyclic ion pair receptors known at the time. The present review is designed to provide a comprehensive and up-to-date overview of the chemistry of macrocycle-based ion pair receptors. We specifically focus on the relationship between structure and ion pair recognition, as well as applications of ion pair receptors in sensor development, cation and anion extraction, ion transport, and logic gate construction.
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Supramolecular chemistry is a central topic in modern chemistry. It touches on many traditional disciplines, such as organic chemistry, inorganic chemistry, physical chemistry, materials chemistry, environmental chemistry, and biological chemistry. Supramolecular hosts, inter alia macrocyclic hosts, play critical roles in supramolecular chemistry. Calix[4]pyrroles, non-aromatic tetrapyrrolic macrocycles defined by sp3 hybridized meso bridges, have proved to be versatile receptors for neutral species, anions, and cations, as well as ion pairs. Compared to the parent system, octamethylcalix[4]pyrrole and its derivatives bearing simple appended functionalities, strapped calix[4]pyrroles typically display enhanced binding affinities and selectivities. In this review, we summarize advances in the design and synthesis of strapped calix[4]pyrroles, as well as their broad utility in molecular recognition, supramolecular extraction, separation technology, ion transport, and as agents capable of inhibiting cancer cell proliferation. Future challenges within this sub-field are also discussed.
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Calixarenos/química , Calixarenos/metabolismo , Porfirinas/química , Porfirinas/metabolismo , Ânions/química , Apoptose , Cátions/química , Permeabilidade da Membrana Celular , Cristalização , Modelos Moleculares , Estrutura Molecular , Compostos Orgânicos/química , Relação Estrutura-Atividade , TermodinâmicaRESUMO
Cancer is among the leading causes of death worldwide. Although a number of new treatment options have been developed in recent years, there remains a need for improved chemotherapies. The primary challenges facing new cancer drugs include: (1) improving patient quality of life, (2) overcoming drug resistance and (3) lowering reoccurrence rates. Major drawbacks of current chemotherapeutics arise from poor selectivity towards cancer cells, dose limiting toxicities, compliance-reducing side effects, and an inability to address resistance mechanisms. Chemotherapeutics that fail to achieve complete eradication of the disease can also lead to relapse and promote treatment resistance. New strategies to overcome these drawbacks include the use of transition metal chelators and ionophores to alter selectively the concentrations of iron, copper, and zinc in cancer cells. A number of metal chelators have successfully demonstrated cytotoxicity and targeted activity against drug-resistant cancer cells; several have proved effective against cancer stem cells, a significant cause of tumour reoccurrence. However, problems with formulation and targeting have been noted. Recent efforts have thus focused on the design of pro-chelators, inactive versions of chelators that are designed to be activated in the tumour. This is an appealing strategy that may potentially increase efficacy towards cancer-resistant malignant cells. This Tutorial Review summarizes recent progress involving transition metal chelators, pro-chelators, and ionophores as potential cancer chemotherapeutics. We will focus on the reported agents that are able to coordinate iron, copper, and zinc.
Assuntos
Quelantes/química , Ionóforos/química , Elementos de Transição/química , Antineoplásicos/química , Antineoplásicos/uso terapêutico , Complexos de Coordenação/química , Complexos de Coordenação/uso terapêutico , Humanos , Neoplasias/tratamento farmacológicoRESUMO
The binding interactions between the azide anion (N3-) and the strapped calix[4]pyrroles 2 and 3 bearing auxiliary hydrogen bonding donors on the bridging moieties, as well as of normal calix[4]pyrrole 1, were investigated via 1H NMR spectroscopic and isothermal titration calorimetry analyses. The resulting data revealed that receptors 2 and 3 have significantly higher affinities for the azide anion in organic media as compared with the unfunctionalized calix[4]pyrrole 1 and other azide receptors reported to date. Single crystal X-ray diffraction analyses and calculations using density functional theory revealed that receptor 2 binds CsN3 in two distinct structural forms. As judged from the metric parameters, in the resulting complexes one limiting azide anion resonance contributor is favored over the other, with the specifics depending on the binding mode. In contrast to what is seen for 2, receptor 3 forms a CsN3 complex in 20% CD3OD in CDCl3, wherein the azide anion is bound only vertically to the NH protons of the calix[4]pyrrole and the cesium cation is complexed within the cone shaped-calix[4]pyrrole bowl. The bound cesium cation is also in close proximity to a naphthobipyrrole subunit present in a different molecule, forming an apparent cation-π complex.
Assuntos
Azidas/química , Calixarenos/química , Pirróis/química , Ligação de Hidrogênio , Modelos Moleculares , Conformação MolecularRESUMO
Synthetic pyrrole-based anion receptors date back to the 1990s. They have been extensively developed in the context of macrocyclic systems as expanded porphyrins and calixpyrroles, and related systems. The chemistry of open-chain pyrrolic systems is, in many respects, no less venerable. It also has more direct analogy to naturally occurring pyrrole-based anion binding motifs. However, it has not been the subject of a comprehensive review. Presented herein is a summary of efforts devoted to the creation of de novo pyrrole-based receptors, as well as the anion recognition chemistry of naturally occurring pyrrolic systems as prodigiosins and their synthetic analogues.
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Using naphthobipyrrole as a functional building block, a new expanded porphyrin, naphthoisoamethyrin, was prepared in 85% yield under acid-catalyzed [4 + 2] MacDonald coupling conditions. Treatment of naphthoisoamethyrin with the nonaqueous uranyl silylamide salt [UO2[N(SiMe3)2]2·2THF] yielded the corresponding uranyl complex. Upon metalation, naphthoisoamethyrin undergoes a two-electron oxidation to yield a formal 22 π-electron aromatic species, as inferred from 1H NMR and UV-vis spectroscopy, as well as cyclic voltammetry.
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Complexation between a water-soluble calix[4]pyrrole and a ditopic pyridine N-oxide derivative in aqueous media produces a bola-type supra-amphiphile that self-assembles to produce higher order morphologies, including multilamellar vesicles and micelles depending on the pH. The present bola-type supra-amphiphile exhibits strong fluorescence due to structural changes and aggregation induced by host-guest complexation. The resulting structures may be used to recognize, encapsulate, and release non-fluorescent, water-soluble small molecules.
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A new approach to the construction of self-assembled structures is reported that is based on ion-pair recognition. Towards this end, the calix[4]pyrrole naphthocrown-4 hybrid structures 2 and 3 were prepared. These multitopic receptors contain recognition sites for both anions and cations. On the basis of solution-phase (1) Hâ NMR spectroscopic analysis and solid-state single-crystal X-ray diffraction structural studies, it was established that receptors 2 and 3 are able to bind specific ion pairs with high selectivity via different binding modes. In the case of CsF and CsCl, the ion-pair complexes formed from receptors 2 and 3 were found to self-assemble to produce either linear supramolecular polymeric crystalline solids or nanotube-like cyclic hexamers depending on the specific choice of ion pairs and crystallization solvents. Proton NMR studies provided evidence for solution-phase self-association in organic media.
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Ion pair receptor 3 bearing an anion binding site and multiple cation binding sites has been synthesized and shown to function in a novel binding-release cycle that does not necessarily require displacement to effect release. The receptor forms stable complexes with the test cesium salts, CsCl and CsNO(3), in solution (10% methanol-d(4) in chloroform-d) as inferred from (1)H NMR spectroscopic analyses. The addition of KClO(4) to these cesium salt complexes leads to a novel type of cation metathesis in which the "exchanged" cations occupy different binding sites. Specifically, K(+) becomes bound at the expense of the Cs(+) cation initially present in the complex. Under liquid-liquid conditions, receptor 3 is able to extract CsNO(3) and CsCl from an aqueous D(2)O layer into nitrobenzene-d(5) as inferred from (1)H NMR spectroscopic analyses and radiotracer measurements. The Cs(+) cation of the CsNO(3) extracted into the nitrobenzene phase by receptor 3 may be released into the aqueous phase by contacting the loaded nitrobenzene phase with an aqueous KClO(4) solution. Additional exposure of the nitrobenzene layer to chloroform and water gives 3 in its uncomplexed, ion-free form. This allows receptor 3 to be recovered for subsequent use. Support for the underlying complexation chemistry came from single-crystal X-ray diffraction analyses and gas-phase energy-minimization studies.