Combinatorial Screening of Water/Proton Permeation of Self-Assembled Pillar[5]arene Artificial Water Channel Libraries

Artificial water channels (AWCs) that selectively transport water and reject ions through bilayer membranes have potential to act as synthetic Aquaporins (AQPs). AWCs can have a similar osmotic permeability, better stability, with simpler manufacture on a larger-scale and have higher functional density and surface permeability when inserted into the membrane. Here, we report the screening of combinatorial libraries of symmetrical and unsymmetrical rim-functionalized PAs A – D that are able to transport ca. 10⁷–10⁸ water molecules/s/channel, which is within 1 order of magnitude of AQPs’ and show total ion and proton rejection. Among the four channels, C and D are 3–4 times more water permeable than A and B when inserted in bilayer membranes. The binary combinations of A – D with different molar ratios could be expressed as an independent (linear ABA ), a recessive (inhibition AB , AC , DB , ACA ), or a dominant (amplification, DBD ) behavior of the water net permeation events.     

基于柱[5]芳烃的超分子组装研究进展

介绍了柱[5]芳烃基于主客体性质和柱状立体结构的超分子组装,以及边缘取代基对柱[5]芳烃的溶解性、功能性和主客体性质的影响。     

四氨基柱[5]芳烃二聚体的合成、结构及性质研究

构象固定的刚性多环主体分子为构筑高级复杂的机械互锁结构提供了重要平台. 为挑战合成刚性多环主体并进一步构筑多层次机械互锁结构, 氧杂杯[4]芳烃桥连的柱[5]芳烃二聚体经过Raney Ni催化氢化还原硝基、与叔丁氧羰基(Boc)-β-丙氨酸缩合和脱去N-Boc保护基三步反应, 生成了四氨基柱[5]芳烃二聚体. X射线单晶衍射实验表明三环目标主体分子具有双桶望远镜形状, 并且构象刚性, 随取代基不同仅有微小变化. 此外, 该四氨基二聚体可作为主体与己二腈形成高稳定性的1∶2络合物. 该研究为制备复杂超分子体系提供了新的机会.     

柱芳烃的合成与应用

综述了近四年来新型超分子主体化合物柱芳烃的合成、发展和应用.其中,柱芳烃及其衍生物的合成主要有两种有机化学合成策略,即"先成环后修饰"和"先修饰后成环".由于这类新型主体化合物具有非常特殊的空间结构和理化性质,目前,它主要应用在主客体包合与分子识别、自组装体系的构筑和智能材料等领域.     

基于柱[5]芳烃主客体包结构筑分子响应型超分子水凝胶

主客体相互作用是在水溶液中与大环主体分子形成稳定的包结物的理想驱动力.以功能化的苯并咪唑衍生物为客体(M),水溶性柱[5]芳烃为主体构建了一种分子响应型超分子水凝胶.通过1H NMR, 2D NOESY和扫描电子显微镜(SEM)研究了水凝胶的成凝胶机理.有趣的是,主客体包结作用、柱[5]芳烃间有序的"外腔"π-π相互作用和分层堆积对于获得超分子水凝胶是必不可少的,非共价键相互作用的动态可逆性使凝胶体系对温度变化/化学刺激产生响应.此外,加入竞争性客体己二腈(ADN)/百草枯(PQ)后,柱[5]芳烃基水凝胶可转化为溶胶.因此,该超分子水凝胶可以选择性识别有机分子.     

1,4-二甲氧基柱[5]芳烃的合成及其与1,6-己二胺包结常数的测定

合成了1,4-二甲氧基柱[5]芳烃（DMP[5]）,采用核磁滴定方法研究了主体分子DMP[5]与客体分子1,6-己二胺的包结作用。通过摩尔比方法确定了主客体分子间的包结比为1∶1,并利用DynaFit计算了包结常数Ka=49 L/mol。本实验可作为有机化学实验在本科生化学及相关专业开设,有利于学生了解超分子化学前沿知识,激发学习兴趣,培养综合实验能力和科研方法。     

Structural Diversification of Pillar[n]arene Macrocycles

Despite the fact that pillar[n]arenes receive major interest as building blocks for supramolecular chemistry and advanced materials, their functionalization is generally limited to the modification of the hydroxy or alkoxy units present on the rims. This limited structural freedom restricts further developments and has very recently been overcome. In this article, we highlight three very recent studies demonstrating further structural diversification of pillar[n]arenes by partial removal of the alkoxy substituents on the rims, which can be considered as the next generation of pillar[n]arenes.     

A Water-Soluble Leggero Pillar[5]arene

The study of aqueous-phase molecular recognition of artificial receptors is one of the frontiers in supramolecular chemistry since most biochemical processes and reactions take place in an aqueous medium and heavily rely on it. In this work, a water-soluble version of leggero pillar[5]arene bearing eight positively charged pyridinium moieties (CWP[5]L) was designed and synthesized, which exhibited good binding affinities with certain aliphatic sulfonate species in aqueous solutions. Significantly, control experiments demonstrate that the guest binding performance of CWP[5]L is superior to its counterpart water-soluble macrocyclic receptor in traditional pillararenes.     

Phenethylamine@Pillar[5]arene Biointerface for Highly Enantioselective Adsorption of Protein

In the life system, the biointerface plays an important role in cell adsorption, platelet adsorption and activation. Therefore, the study of protein adsorption on the biointerface is of great significance for understanding life phenomena and treatment in vitro. In this paper, a chiral biointerface was constructed by the virtue of host‐guest interaction between a water‐soluble pillar[5]arene (WP5) and phenethylamine (PEA) over a gold surface for adsorption of lysozyme proteins. From the experimental results it was identified that the host‐guest biointerface has a high adsorption capacity and strong chiral selectivity. Furthermotre, it was identified that the host‐guest interaction plays the decisive role in the enhancement of chirality of the interface, which was much beneficial for increasing protein adsorption and amplifying the capacity of chiral discrimination. Therefore, this work provides a new idea for the construction of biointerface materials with high protein adsorption capacity and high chiral selectivity through supramolecular interaction, which will have potential applications in the fields of biosensors, biocatalysts, biomaterials.     

An Interesting Approach to Bis-calix[5]arene Analogue from Calix[6]arene

Calix [n] arenas {n = 4, 6 or 8} are easily prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions in one step. It is not surprising that the calyx [n] arene (n = 4, 6, 8) chemistry has been developing very rapidly during the latest 20 years1. However, it is not the case for calixarenes with odd benzene rings (for example, n = 5). The yield of p-tert-butylcalix [5] arene synthesized in one-step from p-tert-butylphenol and formaldehyde was a…     

Positively Charged Nanoaggregates Based on Zwitterionic Pillar[5]arene that Combat Planktonic Bacteria and Disrupt Biofilms

Bacterial biofilms are difficult to eradicate because they are less susceptible to antibiotics and more easily develop resistance. Therefore, there is an urgent need for new materials that can combat planktonic bacteria and disrupt established biofilms. To tackle this challenge, we design a multifunctional zwitterionic pillar[5]arene, which can self‐assemble into weakly positively charged nanoaggregates that exhibit antibacterial activity against Gram‐negative Escherichia coli (DH5α) and Gram‐positive Staphylococcus aureus (SH1000) bacterial strains in solution. In addition, the zwitterionic pillar[5]arene can efficiently disrupt pre‐existing Escherichia coli (DH5α) biofilms and kill the biofilm‐enclosed bacteria without rapid generation of resistance.     

Temperature-Dependent and pH-Responsive Pillar[5]arene-Based Complexes and Hydrogen-Bond-Based Supramolecular Pentagonal Boxes in Water

Supramolecular systems in water are of paramount importance and those based on hydrogen bonds are both intriguing and scarce. Here, after studying the peculiar host–guest complexes formed between per-dimethylamino-pillar[5]arene ( 1 ) and the bis-sulfonates 2 a – c , we describe the formation of the first hydrogen-bond-based supramolecular pentagonal boxes (SPBs), which are stable in water. These pH-responsive SPBs are constructed from 1 as a body, benzene polycarboxylic acids 3 a , b as lid compounds, and 2 a – c as guests. We demonstrate that encapsulation of 2 a – c in pillar[5]arene 1 and in the highly stable water-soluble SPBs, that is, 1(3 a) ₂ and 1(3 b) ₂, is both temperature and pH dependent and, quite interestingly, depends, on the nature of the lid compounds used for capping the boxes even at high pH. We also highlight the difference in the ¹H NMR characteristics of 2 b and 2 c in the cavity of 1 and the SPBs.     

Artificial Water Channels: Towards Biomimetic Membranes for Desalination

Natural Aquaporin (AQP) channels are efficient water translocating proteins, rejecting ions. Inspired by this masterpiece of nature, Artificial Water Channels (AWCs) with controlled functional structures, can be potentially used to mimic the AQPs to a certain extent, offering flexible avenues toward biomimetic membranes for water purification. The objective of this paper is to trace the historical development and significant advancements of current reported AWCs. Meanwhile, we attempt to reveal important structural insights and supramolecular self-assembly principles governing the selective water transport mechanisms, toward innovative AWC-based biomimetic membranes for desalination.     

Diversity Oriented Preparation of Pillar[5]arene-Containing [2]Rotaxanes by a Stopper Exchange Strategy

Rotaxane building blocks bearing 3,5-bis(trifluoromethyl) benzenesulfonate (BTBS) stoppers have been efficiently prepared from a pillar[5]arene derivative, 3,5-bis(trifluoromethyl) benzenesulfonyl chloride (BTBSCl) and different diols, namely 1,10-decanediol and 1,12-dodecanediol. The BTBS moieties of these compounds are good leaving groups and stopper exchange reactions could be achieved by treatment with different nucleophiles thus affording rotaxanes with ester, thioether or ether stoppers.     

Dendritic-Like Molecules Built on a Pillar[5]arene Core as Hole Transporting Materials for Perovskite Solar Cells

Multi-branched molecules have recently demonstrated interesting behaviour as charge-transporting materials within the fields of perovskite solar cells (PSCs). For this reason, extended triarylamine dendrons have been grafted onto a pillar[5]arene core to generate dendrimer-like compounds, which have been used as hole-transporting materials (HTMs) for PSCs. The performances of the solar cells containing these novel compounds have been extensively investigated. Interestingly, a positive dendritic effect has been evidenced as the hole transporting properties are improved when going from the first to the second-generation compound. The stability of the devices based on the best performing pillar[5]arene material has been also evaluated in a high-throughput ageing setup for 500 h at high temperature. When compared to reference devices prepared from spiro-OMeTAD, the behaviour is similar. An analysis of the economic advantages arising from the use of the pillar[5]arene-based material revealed however that our pillar[5]arene-based material is cheaper than the reference.     

Polycationic Pillar[5]arene Derivatives: Interaction with DNA and Biological Applications

Dendritic pillar[5]arene derivatives have been efficiently prepared by grafting dendrons with peripheral Boc‐protected amine subunits onto a preconstructed pillar[5]arene scaffold. Upon cleavage of the Boc‐protected groups, water‐soluble pillar[5]arene derivatives with 20 ( 13 ) and 40 ( 14 ) peripheral ammonium groups have been obtained. The capability of these compounds to form stable nanoparticles with plasmid DNA has been demonstrated by gel electrophoresis, transmission electron microscopy (TEM), and dynamic light scattering (DLS) investigations. Transfection efficiencies of the self‐assembled 13 /pCMV‐Luc and 14 /pCMV‐Luc polyplexes have been evaluated in vitro with HeLa cells. The transfection efficiencies found for both compounds are good, and pillar[5]arenes 13 and 14 show very low toxicity if any.     

Grafting Dendrons onto Pillar[5]Arene Scaffolds

With their ten peripheral substituents, pillar[5]arenes are attractive compact scaffolds for the construction of nanomaterials with a controlled number of functional groups distributed around the macrocyclic core. This review paper is focused on the functionalization of pillar[5]arene derivatives with small dendrons to generate dendrimer-like nanomaterials and bioactive compounds. Examples include non-viral gene vectors, bioactive glycoclusters, and liquid-crystalline materials.     

Aggregation Mode,Host-Guest Chemistry in Water,and Extraction Capability of an Uncharged,Water-Soluble,Liquid Pillar[5]arene Derivative

An uncharged, water-soluble per-ethylene-glycol pillar[5]arene derivative ( 1 ) was synthesized and its aggregation mode, host-guest chemistry in water and extraction ability was explored. Compound 1 is a liquid at room temperature; in water, limited self-aggregation occurred at high concentrations as deduced from diffusion NMR and dynamic light scattering. Compound 1 forms pseudo-rotaxane-like 1 : 1 host-guest complexes with 1,ω-di-substituted alkanes with association constants on the order of 10³–10⁴ m ⁻¹. Interestingly, NMR experiments showed that the guest location relative to the host ring system differs among the different complexes. In proof-of-concept experiments, compound 1 was shown to extract structurally related organic compounds from benzene into water with significant selectivity. Compound 1 , which is a liquid at room temperature and has only limited interactions with its side arms, can, in principle, be regarded as a complement to or as a kind of type I porous liquid.     

Water‐Soluble Pillar[n]arene Mediated Supramolecular Self‐Assembly: Multi‐Dimensional Morphology Controlled by Host Size

We report tunable supramolecular self‐assemblies formed by water‐soluble pillar[n]arenes ( WPn s, n=5–7) and bipyridinium‐azobenzene guests. Nanoscale or microscale morphology of self‐assemblies in water was controlled by the host size of WPn . Supramolecular self‐assemblies could undergo morphology conversion under irradiation with UV light.