Macrocyclic arenes including calixarenes, resorcinarenes, cyclotriveratrylene, pillararenes and so on have emerged as highly attractive synthetic macrocyclic hosts due to their unique structures, ...facile functionalization, and broad range of applications. In recent years, there has been growing interest in the development of novel macrocyclic arenes composed of various aromatic building blocks bridged by methylene groups, which have found applications in various research areas. Consequently, the development of novel macrocyclic arenes has become a frontier and hot topic in supramolecular and macrocyclic chemistry. In this review, we feature the recent advances in the synthesis and applications of novel macrocyclic arenes that have emerged in the last decade. The general synthetic strategies employed for these macrocyclic arenes are systematically summarized, and their wide applications in molecular recognition and assemblies, molecular machines, biomedical science and functional materials are highlighted.
In this review, we summarize the recent advances in newly reported macrocyclic arenes, focusing on their synthetic strategies and applications.
Abstract
Supramolecular tessellation has gained increasing interest in supramolecular chemistry for its structural aesthetics and potential applications in optics, magnetics and catalysis. In this ...work, a new kind of supramolecular tessellations (STs) have been fabricated by the exo-wall interactions of pagoda4arene (P4). ST with rhombic tiling pattern was first constructed by P4 itself through favorable π···π interactions between anthracene units of adjacent P4. Notably, various highly ordered STs with different tiling patterns have been fabricated based on exo-wall charge transfer interactions between electron-rich P4 and electron-deficient guests including 1,4-dinitrobenzene, terephthalonitrile and tetrafluoroterephthalonitrile. Interestingly, solvent modulation and guest selection played a crucial role in controlling the molecular arrangements in the co-crystal superstructures. This work not only proves that P4 is an excellent macrocyclic building block for the fabrication of various STs, but also provides a new perspective and opportunity for the design and construction of supramolecular two-dimensional organic materials.
Pagoda[4]arene and i‑Pagoda[4]arene Han, Xiao-Ni; Han, Ying; Chen, Chuan-Feng
Journal of the American Chemical Society,
05/2020, Letnik:
142, Številka:
18
Journal Article
Recenzirano
A new type of macrocyclic arenes, named pagoda4arene (P4) and i-pagoda4arene (i-P4), were conveniently synthesized by the TFA-catalyzed one-pot condensation of 2,6-dimethoxylanthracene and ...paraformaldehyde in dichloromethane at room temperature. P4 and i- P4 showed unique square pagoda structures and fixed conformations in solution and also exhibited strong blue fluorescence. Moreover, P4 and i-P4 with deep and rich-electron cavities could not only encapsulate n-hexane and one or two dichloromethane molecules in the solid state but also showed strong binding abilities toward neutral dinitriles with different chain lengths and various nitrogen-containing heterocyclic salts to form 1:1 stable host–guest complexes in both solution and the solid state. In particular, it was also found that with the increase in the alkyl chain length of the dinitriles, the association constants for their complexes with both P4 and i-P4 were markedly increased from glutaronitrile to octanedinitrile as a result of the deep cavities of the macrocycles and multiple intermolecular interactions. Since P4 and i- P4 had stable planar chirality, their efficient resolutions were further achieved by HPLC with a chiral column. Interestingly, the two enantiomers showed mirror-imaged CD signals and excellent CPL properties, which could allow them to have potential applications in chiral luminescent materials.
Development of circularly polarized luminescence (CPL) materials utilizing supramolecular strategies has recently attracted increasing interest in supramolecular chemistry and materials science. ...Chiral macrocycles, especially chiral macrocyclic hosts, have stable structures, adjustable internal cavities to encapsulate different guests, and host-guest complexation to induce special photophysical properties. Consequently, various CPL materials based on chiral macrocycles have been developed during the last decade. To gain a better understanding of this rapidly developing research area, it is necessary and also important to summarize the advances in CPL materials based on chiral macrocycles. In this review, CPL materials from different chiral macrocycles, especially classical and newly reported chiral macrocyclic hosts and their derivatives, will be comprehensively summarized. It is believed that this review will be of guiding significance and also very helpful for the development of macrocyclic chemistry and CPL materials.
This review comprehensively summarizes circularly polarized luminescence materials from chiral macrocycles, especially chiral macrocyclic hosts and their derivatives.
Background and Objectives
In this retrospective study, we examined the CA17 tissue expression and analyzed its clinical significance in cholangiocarcinoma (CCA).
Materials and Methods
...Immunohistochemistry was performed to assess CA17 expression on tissue microarrays in a training cohort enrolling 120 CCA patients and a validation cohort comprising 60 CCA patients. Image pro plus was applied to score the staining intensity and expression level of CA17 marker. Kaplan‐Meier analysis, Cox's proportional hazards regression, and nomogram were applied to evaluate the prognostic significance of CA17.
Results
CA17 cancer biomarker over‐expression was significantly observed in CCA compared to their non‐tumor counterparts, and positively correlated with aggressive tumor phenotypes, like lymph node metastasis. Meanwhile, patients with high expression of CA17 correlated with worse postoperative overall survival (OS) and recurrence‐free survival. Besides, multivariate analysis identified that CA17 expression was an independent prognostic factor for cholangiocarcinoma patients, which indicated that the CA17 could be more efficient than serum CA19‐9 in predicting the OS of CCA patients. Notably, the nomogram integrating CA17 expression had better prognostic performance as compared with current TNM staging systems.
Conclusion
CA17 was an independent adverse prognostic factor for CCA patients’ survival, which may serve as a promising prognostic biomarker for CCA patients.
Despite macrocyclic arene chemistry has achieved rapid development in recent years, the synthesis of new macrocyclic arenes from the aromatic rings with no directing groups remains a considerable ...challenge. In this work, a new type of macrocyclic arene, naphth4arene (NA4A), composed of four naphthalene rings bridged by methylene groups, was successfully synthesized by a macrocycle-to-macrocycle conversion strategy. NA4A shows 1,3-alternate and 1,2-alternate conformations in solid state, and they can be selectively obtained. By supramolecular co-assembly of NA4A and 1,2,4,5-tetracyanobenzene (TCNB) in different concentrations and ambient temperatures, two conformation-dependent crystalline luminescent co-assemblies 1,2-NTC and 1,3-NTC can be selectively prepared as well. Interestingly, the two charge transfer crystalline assemblies containing NA4A with different conformation emit bright yellow and green fluorescence, respectively, and also display high photoluminescence quantum yields (PLQYs) of 45% and 43%. Furthermore, the two crystalline assemblies can exhibit color-tunable two-photon excited upconversion emission property. This work provides a new perspective and route for fabricating color-tunable supramolecular crystalline luminescent materials regulated by the conformations of macrocyclic arene.
Study of enantioselective recognition in water by synthetic chiral macrocyclic receptors is undoubtedly of theoretical and practical significance, but it is a big challenge to achieve the ...enantioselective recognition with both high enantioselectivity and high affinity in water probably due to the deficiency of such water‐soluble macrocyclic receptors with stable chiral cavities. Herein, we report a new class of chiral macrocyclic arenes named octopus3arenes. The enantiomeric macrocycles are composed of three homochiral ethenoanthracene subunits, and they can be synthesized by two pathways and then easily converted into water‐soluble octopus3arenes P‐1 and M‐1. Notably, P‐1 and M‐1 with the rigid hexagonal structures and stable chiral hydrophobic cavities exhibit highly enantioselective recognition towards three pairs of chiral ammonium salts in water with the association constant up to 106 M−1 and the S/R selectivity up to 12.89.
Enantiomeric water‐soluble octopus3arenes with rigid hexagonal structures and stable chiral hydrophobic cavities were easily synthesized. They exhibited highly enantioselective recognition towards three pairs of chiral ammonium salts in water with the association constant up to 106 and the S/R selectivity up to 12.89.
A pair of inherently chiral belt-shaped conjugated macrocycles were conveniently synthesized starting from 2,7-fluoren3arene triflate, and they not only exhibited green fluorescence, but also showed ...circularly polarized luminescence with a |
g
lum
| of 2.0 × 10
−3
.
A pair of inherently chiral belt-shaped conjugated macrocycles were synthesized, and they showed strong fluorescence and circularly polarized luminescence properties.
Chirality‐driven self‐sorting plays an essential role in controlling the biofunction of biosystems, such as the chiral double‐helix structure of DNA from self‐recognition by hydrogen bonding. ...However, achieving precise control over the chiral self‐sorted structures and their functional properties for the bioinspired supramolecular systems still remains a challenge, not to mention realizing dynamically reversible regulation. Herein, we report an unprecedented saucer4arene‐based charge transfer (CT) cocrystal system with dynamically reversible chiral self‐sorting synergistically induced by chiral triangular macrocycle and organic vapors. It displays efficient chain length‐selective vapochromism toward alkyl ketones due to precise modulation of optical properties by vapor‐induced diverse structural transformations. Experimental and theoretical studies reveal that the unique vapochromic behavior is mainly attributed to the formation of homo‐ or heterochiral self‐sorted assemblies with different alkyl ketone guests, which differ dramatically in solid‐state superstructures and CT interactions, thus influencing their optical properties. This work highlights the essential role of chiral self‐sorting in controlling the functional properties of synthetic supramolecular systems, and the rarely seen controllable chiral self‐sorting at the solid‐vapor interface deepens the understanding of efficient vapochromic sensors.
A chiral macrocycle‐based cocrystal system that undergoes dynamically reversible chiral self‐sorting displays efficient chain length‐selective vapochromism to alkyl ketones. The unique vapochromic behavior was mainly due to different solid‐state superstructures and noncovalent interactions from the homo‐ or heterochiral self‐assembly.
Background and Aims
Cancer cell survival depends on the balance between reactive oxygen species production and scavenging, which is regulated primarily by NRF2 during tumorigenesis. Here, we ...demonstrate that deletion of RBP5‐mediating protein (RMP) in an autonomous mouse model of intrahepatic cholangiocarcinoma (ICC) delays tumor progression.
Approach and Results
RMP‐overexpressing tumor cells exhibited enhanced tolerance to oxidative stress and apoptosis. Mechanistically, RMP competes with NRF2 for binding to the Kelch domain of KEAP1 (Kelch‐like ECH‐associated protein 1) through the E**E motif, leading to decreased NRF2 degradation via ubiquitination, thus increasing NRF2 nuclear translocation and downstream transactivation of antioxidant genes. This RMP‐KEAP1‐NRF2 axis promotes ICC tumorigenesis, metastasis, and drug resistance. Consistent with these findings, the RMP level in human ICC is positively correlated with the protein level of NRF2 and is associated with poor prognosis.
Conclusion
These findings reveal that RMP is involved in the oxidative stress defense program and could be exploited for targeted cancer therapies.
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