New Insights into the Ion-Specific Behaviors and Design Strategies for Ion–π Interactions

Liu, Zhangyun; Chen, Zheng; Xu, Xin

doi:10.31635/ccschem.020.202000285

Cited by 15 publications

(8 citation statements)

References 67 publications

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“…It was suggested that cation−π interactions are essentially electrostatic attractions. , To date, the electrostatic model is still one of the popular tools to predict the binding ability of new cation−π systems. Considering the complex physics and multiple influencing factors of cation−π interactions, various methods, such as density functional theory, second-order Møller–Plesset perturbation theory, and Hartree–Fock theory, have also been applied to investigate cation−π interaction energies. − According to computer simulations, the binding energies of model systems for different cations follow the trend of Mg 2+ > Ca 2+ > Li + > Na + > K + ≈ NH 4 + > NMe 4 + in the gas phase . Moreover, the theoretical strength of cation−π interactions is two times larger than that of salt bridges in aqueous media, highlighting their importance for protein engineering …”

Section: Characterization and Modulating Parameters Of Cation−π Inter...mentioning

confidence: 99%

Principles of Cation−π Interactions for Engineering Mussel-Inspired Functional Materials

et al. 2022

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Conspectus Supramolecular assembly is commonly driven by noncovalent interactions (e.g., hydrogen bonding, electrostatic, hydrophobic, and aromatic interactions) and plays a predominant role in multidisciplinary research areas ranging from materials design to molecular biology. Understanding these noncovalent interactions at the molecular level is important for studying and designing supramolecular assemblies in chemical and biological systems. Cation−π interactions, initially found through their influence on protein structure, are generally formed between electron-rich π systems and cations (mainly alkali, alkaline-earth metals, and ammonium). Cation−π interactions play an essential role in many biological systems and processes, such as potassium channels, nicotinic acetylcholine receptors, biomolecular recognition and assembly, and the stabilization and function of biomacromolecular structures. Early fundamental studies on cation−π interactions primarily focused on computational calculations, protein crystal structures, and gas- and solid-phase experiments. With the more recent development of spectroscopic and nanomechanical techniques, cation−π interactions can be characterized directly in aqueous media, offering opportunities for the rational manipulation and incorporation of cation−π interactions into the design of supramolecular assemblies. In 2012, we reported the essential role of cation−π interactions in the strong underwater adhesion of Asian green mussel foot proteins deficient in l-3,4-dihydroxyphenylalanine (DOPA) via direct molecular force measurements. In another study in 2013, we reported the experimental quantification and nanomechanics of cation−π interactions of various cations and π electron systems in aqueous solutions using a surface forces apparatus (SFA). Over the past decade, much progress has been achieved in probing cation−π interactions in aqueous solutions, their impact on the underwater adhesion and cohesion of different soft materials, and the fabrication of functional materials driven by cation−π interactions, including surface coatings, complex coacervates, and hydrogels. These studies have demonstrated cation−π interactions as an important driving force for engineering functional materials. Nevertheless, compared to other noncovalent interactions, cation−π interactions are relatively less investigated and underappreciated in governing the structure and function of supramolecular assemblies. Therefore, it is imperative to provide a detailed overview of recent advances in understanding of cation−π interactions for supramolecular assembly, and how these interactions can be used to direct supramolecular assembly for various applications (e.g., underwater adhesion). In this Account, we present very recent advances in probing and applying cation−π interactions for mussel-inspired supramolecular assemblies as well as their structural and functional characteristics. Particular attention is paid to experimental characterization techniques for quantifying cation−π interactions in aqueous s...

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Section: Characterization and Modulating Parameters Of Cation−π Inter...mentioning

confidence: 99%

Principles of Cation−π Interactions for Engineering Mussel-Inspired Functional Materials

et al. 2022

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“…Here we aim to provide a wide-scope molecular tool to quantify and picture the different binding behavior in anion- interacting systems. The current design is based on the use of benzene triimide (BTI) 34 and the theoretical guidance for ion- interactions, 39 following three considerations: 1) BTI bearing a high quadruple moment (Q ZZ = 14.5 B) enables enhanced anion- interactions; 2) the extending surface of BTI provides multiple binding sites (both the six-and five-membered rings are available to accept an anion), which should be advantageous for accommodation of differently-shaped and polydentate anions; 3) appropriate separation between the two BTI planes is crucial: A small distance is good for achieving high specificity toward given anions like N 3as previously demonstrated with the small cage 1, 34 while a too large distance would weaken the additivity or cooperativity. Thus, a triangular prism cage 2 with BTI as the bases, 2,7naphthalene dimethyl as the spacers is designed (Figure 2).…”

Section: Introductionmentioning

confidence: 99%

Naphthalene-Pillared Benzene Triimide Cage: An Efficient Receptor for Polyhedral Anions and a General Tool for Probing Theoretically-Existing Anion-π Binding Motifs

Tuo¹,

Ao²,

Wang³

et al. 2022

CCS Chem

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A triangular prism cage 2 with benzene triimide (BTI) as the bases, 2,7-naphthalene dimethyl as the supporting pillars was designed and synthesized efficiently. The two parallel BTI planes constitute a cavity of 7.58 Å which allows inclusion of anions of various sizes. Cage 2 showed so far the strongest binding affinity to a series of polyhedral (tetrahedral and octahedral) anions including PF 6 -(24651 M -1 ), ClO 4 -(28234 M -1 ), CH 3 SO 3 -(30571 M -1 ), BF 4 -(31613 M -1 ) and HSO 4 -(84623 M -1 ). The obtained eleven crystal structures of 2⸧Xcomplexes with different anions demonstrated that multiple and cooperative anion- interactions contribute synergistically to the strong complexation. The series of complex structures systematically suggested that cage 2 is a good, general tool for probing anion- binding motifs that have only been predicted in theoretical calculations. For anions of triangular (NO 3 -) and polyhedral (BF 4 -, ClO 4 -, PF 6 -) shapes, the as-predicted most stable anion- binding motifs with charge-neutral  systems were experimentally observed for the first time.

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“…Hence, the cationic CPs with quaternary ammonium groups could attach and insert the bacterial membrane via electrostatic and hydrophobic interactions. It has been reported that the hydrophobic interaction is hard to affect the zeta potential of bacteria, yet the electrostatic interaction would cause a positive potential shift ( 38 ). The remarkable potential change of the PMNT/ S. oneidensis group was attributed to the electrostatic interaction.…”

Section: Resultsmentioning

confidence: 99%

Flexible bioelectronic device fabricated by conductive polymer–based living material

Wang

Bai

et al. 2022

Sci. Adv.

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Living materials are worked as an inside collaborative system that could naturally respond to changing environmental conditions. The regulation of bioelectronic processes in living materials could be effective for collecting biological signals and detecting biomarkers. Here, we constructed a living material with conjugated polymers poly[3-(3′- N , N , N -triethylamino-1′-propyloxy)-4-methyl-2,5-thiophene chloride] (PMNT) and Shewanella oneidensis MR-1 biofilm. In addition, the living material was integrated as a flexible bioelectronic device for lactate detection in physiological fluids (sweat, urine, and plasma). Owing to the electroconductivity of conjugated polymers, PMNT could optimize the bioelectronic process in the living material. The collected electrical signal could be wirelessly transferred to a portable smartphone for reading and analyzing. Because lactate is also a biomarker for cancer treatment, the flexible bioelectronic device was further used to detect and count the cancer cells. The proof of the bioelectronic device using conductive polymer–based living material exhibits promising applications in the next-generation personal health monitoring systems.

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New Insights into the Ion-Specific Behaviors and Design Strategies for Ion–π Interactions

Cited by 15 publications

References 67 publications

Principles of Cation−π Interactions for Engineering Mussel-Inspired Functional Materials

Principles of Cation−π Interactions for Engineering Mussel-Inspired Functional Materials

Naphthalene-Pillared Benzene Triimide Cage: An Efficient Receptor for Polyhedral Anions and a General Tool for Probing Theoretically-Existing Anion-π Binding Motifs

Flexible bioelectronic device fabricated by conductive polymer–based living material

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