Calixarenes (CAs), featuring unique cavity architectures and exceptional host-guest capabilities, provide an attractive molecular platform for tailoring ion coordination and transport behaviors in solid-state electrolytes (SSEs). Despite these structural advantages, their potential in SSEs has been rarely explored. Herein, we design a calix[6]arene-functionalized (C6A) polymer quasi-solid electrolyte (PECQSE) via insitu polymerization, in which a cross-linked matrix is formed between urethane-functionalized poly(ethylene oxide) (PEG-IEM) and ethoxylated trimethylolpropane triacrylate (ETPTA). The incorporation of C6A establishes a size-selective, interaction-dominated ion-regulation framework, in which bulky TFSI- exhibit restricted mobility, while Li+ transport is facilitated along conduction pathways, resulting in Li+ transference number of 0.76. Meanwhile, hydrogen-bonding interactions between C6A phenolic hydroxyl groups and urethane segments suppress PEG crystallinity and promote LiTFSI dissociation. These interactions facilitate interfacial LiTFSI reduction and support the formation of a LiF/Li2O-rich SEI, which guides uniform lithium deposition and suppresses dendrite growth. Consequently, Li|Li symmetric cells exhibit ultralong cycling stability exceeding 7000h with low polarization and high-loading LiFePO4|Li full cells retain 80.6% capacity after 700 cycles at 2 C. The assembled 1 Ah pouch cell delivers excellent safety and durability with 91.8% retention after 240 cycles, demonstrating an effective interfacial engineering strategy for next-generation lithium metal batteries.

Computational study of interaction of calixarene with ebola virus structural proteins and its potential therapeutic implications.

This work presents for the first time the modification and enhancement of sensory properties of a chemoresistive conductive core-shell nanocomposite of multi-walled carbon nanotubes (MWCNTs) and polypyrrole (PPy) doped by p-toluenesulfonate anions (TS) (MWCNT/PPy-TS) under long ultrasonic treatment in joint dispersions and, hence, under physico-chemical interactions with functionalized calixarenes (CA), namely calix[4]arene methylene-bis-phosphonic acid octasodium salt (CPA) and calix[4]arene sulfonic acid (CSA). The interactions are confirmed by a detailed analysis of FTIR spectra of a parent binary MWCNT/PPy-TS nanocomposite and its counterpart ternary MWCNT/PPy-TS/CA nanocomposites as well as by sensor measurements. The results of the latter show a strong enhancement of the sensitivity of the MWCNT/PPy-TS to isopropanol, acetone and ammonia vapors due to CSA and CPA additives, which, however, depends on the nature of functional groups of these CA.

Macrocycles composed of diverse aromatic or nonaromatic structures, such as cyclodextrins (CDs), calixarenes (CAs), cucurbiturils (CBs), and pillararenes (PAs), have garnered significant attention due to their inherent advantages of possessing cavity structures, unique functional groups, and facile modification. Due to these distinctive features enabling them to facilitate ion insertion and extraction, form crosslinked porous structures, offer multiple redox-active sites, and engage in host-guest interactions, macrocycles have made huge contributions to electrochemical energy storage and conversion (EES/EEC). Here, we have summarized the recent advancements and challenges in the utilization of CDs, CAs, CBs, and PAs as well as other novel macrocycles applied in EES/EEC devices. The molecular structure, properties, and modification strategies are discussed along with the corresponding energy density, specific capacity, and cycling life properties in detail. Finally, crucial limitations and future research directions pertaining to these macrocycles in electrochemical energy storage and conversion are addressed. It is hoped that this review is able to inspire interest and enthusiasm in researchers to investigate macrocycles and promote their applications in EES/EEC.

Photodynamic therapy as a burgeoning and non-invasive theranostic technique has drawn great attention in the field of antibacterial treatment but often encounters undesired phototoxicity of photosensitizers during systemic circulation. Herein, a supramolecular substitution strategy is proposed for phototherapy of drug-resistant bacteria and skin flap repair by using macrocyclic p-sulfonatocalix(4)arene (SC4A) as a host, and two cationic aggregation-induced emission luminogens (AIEgens), namely TPE-QAS and TPE-2QAS, bearing quaternary ammonium group(s) as guests. Through host-guest assembly, the obtained complex exhibits obvious blue fluorescence in the solution due to the restriction of free motion of AIEgens and drastically inhibits efficient type I ROS generation. Then, upon the addition of another guest 4,4'-benzidine dihydrochloride, TPE-QAS can be competitively replaced from the cavity of SC4A to restore its pristine ROS efficiency and photoactivity in aqueous solution. The dissociative TPE-QAS shows a high bacterial binding ability with an efficient treatment for methicillin-resistant Staphylococcus aureus (MRSA) in dark and light irradiation. Meanwhile, it also exhibits an improved survival rate for MRSA-infected skin flap transplantation and largely accelerates the healing process. Thus, such cascaded host-guest assembly is an ideal platform for phototheranostics research.

Metal sulfide sub-nanometer clusters formed within calix(8)arene Langmuir-Blodgett films

Abstract In bio‐medical field, one of the most challenging hurdles connected with development of therapeutics is the efficient transport and delivery of drugs to the infected cells of human body. Supramolecular chemistry provides innovative designs for effective biological applications such as drug and gene delivery. In various applications of supramolecular chemistry, macrocyclic molecules such as calixarenes, cyclodextrins, cucurbiturils, and pillar arenes serve as ideal hosts that can bind guest molecules based on the electron density and size of their cavities. This review focuses on the recent advancements in major supramolecular systems such as calixarenes (CA), curcurbiturils (CB), cyclodextrins (CD) and pillar[n] arenes (PAs). Owing to their non‐covalent interactions and adaptive capability, these supramolecular‐based nucleic acid delivery systems provide customized treatment options in cancer therapy. These supramolecular carriers are distinct due to their capacity to functionalize and alter their structure in accordance with the required application. The use of such amphiphilic macromolecules as a carrier for gene transfection have been thoroughly investigated leading to advancements in therapeutic research. The aim of this review is to highlight and showcase the endeavours of utilising supramolecular systems in drug/nucleic acid delivery.

Light-harvesting, which involves the conversion of sunlight into chemical energy by natural systems such as plants, bacteria, is one of the most universal routine activities in nature. Thus far, various artificial light-harvesting systems (LHSs) have been fabricated toward solar energy utilization through mimicking natural photosynthesis in simplified and altered ways. Macrocycles are supramolecular hosts with unique cavities, in which specific guest molecules can be recognized based on non-covalent interactions. They have been widely employed in constructing LHSs due to their ability to form supramolecular assembly and dynamic molecular activity. In this review, we mainly focus on some representative examples reported by our group and other groups. Specifically, the fabrication of LHSs and their related discussions, such as a high donor/acceptor ratio, driving force for the formation of supramolecular assemblies and energy transfer mechanisms using different water-soluble macrocycles such as cyclodextrins (CD), pillararenes (PA), calixarenes (CA), cucurbiturils (CB), and other macrocycles will be included. In addition, how the resulting supramolecular self-assembled LHSs could be potentially utilized for photocatalysis, sensing, and imaging is also explained in detail. Challenges and developing trends for photochemical solar energy conversion will also be presented.

The imbalance of amyloid-β (Aβ) production and clearance causes aggregation of Aβ1-42 monomers to form fibrils and amyloid plaques, which is an indispensable process in the pathogenesis of Alzheimer's disease (AD), and eventually leads to pathological changes and cognitive impairment. Consequently, Aβ1-42 is the most important target for the treatment of AD. However, developing a single treatment method that can recognize Aβ1-42 , inhibit Aβ1-42 fibrillation, eliminate amyloid plaques, improve cognitive impairments, and alleviate AD-like pathology is challenging. Here, a coassembly composed of cyclodextrin (CD) and calixarene (CA) is designed, and it is used as an anti-Aβ therapy agent. The CD-CA coassembly is based on the previously reported heteromultivalent recognition strategy and is able to successfully eliminate amyloid plaques and degrade Aβ1-42 monomers in 5xFAD mice. More importantly, the coassembly improves recognition and spatial cognition deficits, and synaptic plasticity impairment in the 5xFAD mice. In addition, the coassembly ameliorates AD-like pathology including prevention of neuronal apoptosis and oxidant stress, and alteration of M1/M2 microglial polarization states. This supramolecular approach makes full use of both molecular recognition and self-assembly of macrocyclic amphiphiles, and is a promising novel strategy for AD treatment.

Calixarenes (CAs), representing the third generation of supramolecular hosts and one of the most widely studied macrocyclic scaffolds, offer (almost) unlimited structure and application possibilities due to their ease of modification, which allows one to establish a large molecular library as a material basis for diverse biomedical applications. Moreover, CAs and their derivatives engage in various noncovalent interactions for the facile recognition of guests including bioactive molecules and are also important building blocks for the fabrication of supramolecular architectures. In view of their molecular recognition and self-assembly properties, CAs are extensively applied in biosensing, bioimaging, and drug/gene delivery. Additionally, some CA derivatives exhibit biological activities and can therefore be used as new therapeutic agents. Herein, we summarize the diverse biomedical applications of CAs including in vitro diagnosis (biosensing), in vivo diagnosis (bioimaging), and therapy.

ABSTRACT A de-tert-butyl calix arene phosphate (DCAP) with a complete elimination of the upper edge and a complete substitution of the lower edge was synthesized by dealkylation and substitution reactions. The chemical structure of DCAP was further characterized by FTIR, mass MS and 1 H NMR. The ability of DCAP to extract light rare earth ions was studied as a function of concentration, aqueous phase pH, phase ratio, and extraction time. The results showed that DCAP had a 4% higher extraction rate of Pr3+ compared to Nd3+ under the same conditions. Preliminary extraction mechanism was also investigated.

Calixarene Based Ligands for Radium and Barium

Hexaacetato Calix (6) arene as a novel extractant in the recovery of Cerium (III) by liquid-liquid extraction

Calixarene Based Ligands for Radium and Barium

The properties of CoFe2O4@Calix [8] Core-Shell as a novel catalysthasbeen investigatedto compare with well-known catalyst“Fe3O4@Silica”. It has been shown that CoFe2O4 magnetite particle can be use as important catalyst inside the calix ring.In our previous papersgood resultshave been yielded and exhibited about the BnNn ring properties and CoFe2O4@BnNn. In present work it has been shown there is anon-covalent attractionbetween CoFe2O4and calix [8] coated molecules. The Physical-chemistry properties such asenergy densities,potential energy densities,electron densities, ELF, LOL,eta index, elasticity ofelectron density and ECPforCoFe2O4@calix[8] shell have been calculated and simulated in related reactions for those groupsfunctionalized.

Abstract The [2+2] photocycloaddition (PCA [2+2]) of alkenes is one of the most synthetically useful photoreactions. It is a convenient one‐step reaction that is useful for generating substituted cyclobutanes, polymers, and biologically relevant molecules. However, the reaction efficiency is limited by its bimolecular nature requiring encounter between two reactants within the narrow window of excited state lifetime of the photoactive alkene, and competition from the unimolecular photoisomerization. Our groups have utilized macrocyclic cavitands, especially cucurbiturils(CB), to confine two alkene molecules within their cavities and steer them towards a single dimer regio‐ and stereoselectively. Although, primarily the review focuses on photocycloaddition within CBs, such reactions in closely related cavitands such as cyclodextrins (CD) and calixarenes (CA) are also briefly mentioned to provide a comparison with CBs. Studies on photocycloaddition of olefins within CB by other research groups are also briefly highlighted. A mechanistic model, with ability to predict the nature of the dimer product formed within the above reaction containers is included.

Calix(4)arene sulfonic acid complexes with halogenated acetic acids

Undecahydro-mercapto-closo-dodecaborate (BSH), a purely inorganic cluster anion, serves as an unconventional stabilizing ligand for the preparation of gold nanoparticles (AuNPs). The BSH-capped AuNPs serve as nano-scaffolds, allowing for the creation of supramolecular architectures by using polycationic macrocyclic host molecules, through strong host-guest complexation. An amphiphilic calixarene (CX) forms first mono- and subsequently bi-layer assemblies on the BSH-AuNP surfaces depending on the CX concentration. The inorganic-organic hybrid materials, combined with host-dye displacement assays, serve as a chemosensing ensemble for negatively charged molecules, including DNA.

Photochemistry along with life as we know it originated on earth billions of years ago. Supramolecular Photochemistry had its beginning when plants that sustain life began transforming water into oxygen by carrying out light initiated reactions within highly organized assemblies. Prompted by the efforts of J. Priestly (photosynthesis), F. Sestini, S. Cannizaro, and C. Liebermann (solid-state photochemistry of santonin, quinones, and cinnamic acid), orderly scientific investigations of the link between light absorption by matter and molecules and the chemical and physical consequences began in the mid-1700s. By 1970 when Molecular Photochemistry had matured, it was clear that controlling photochemical reactions by conventional methods of varying reaction parameters like temperature and pressure would be futile due to the photoreactions' very low activation energies and enthalpies. During the last 50 years, the excited state behavior of molecules has been successfully manipulated with the use of confining media and weak interactions between the medium and the reactant molecule. In this context, with our knowledge from experimentation with micelles, cyclodextrins (CD), cucurbitruils (CB), calixarenes (CA), Pd nanocage, crystals, and zeolites as media, we began about a decade ago to explore the use of a new water-soluble synthetic organic cavitand, octa acid (OA) as a reaction container. The uniqueness of OA as an organic cavitand lies in that two OA molecules form a closed hydrophobic capsule to encapsulate water-insoluble guest molecule(s). The ability to include a large number of guest molecules in OA has provided an opportunity to examine the excited state chemistry of organic molecules in a hydrophobic, confined environment. OA distinguishes itself from the well-known cavitands CD and CB by its active reaction cavity absorbing UV-radiation between 200 and 300 nm and serving as energy, electron, and hydrogen donor. The freedom of guest molecules in OA, between that in crystals and isotropic solution can be transformed into photoproducts selectivity. The results of our photochemical investigations elaborated in this Account demonstrate that OA with a medium sized cavity exerts better control on excited state processes than the more common and familiar organic hosts such as CD, CB, CA, and micelles. By examining the photochemistry of a number of molecules (olefins, carbonyls, aromatics and singlet oxygen) that undergo varied reactions (cleavage, cycloaddition, cis-trans isomerization, oxidation and cyclization) within OA capsule, we have demonstrated that the free space within the container, the capsule influenced conformation and preorientation of guest molecules, supramolecular steric control, and capsular dynamics contribute to the altered excited state behavior. In this Account, we have shown that photochemistry based on concepts of physical organic and supramolecular chemistry continues to be a discipline with unlimited potential. The future of supramolecular photochemistry lies in synthetic, materials, medicinal, and biological chemistries. Success in these areas depends on synthesizing well-designed water-soluble hosts that can emulate complex biological assemblies, organizing and examining the behavior of supramolecular assemblies on solid surfaces, rendering the photoreactions catalytic, and delivering encapsulated drugs in a targeted fashion.

Quantum chemical calculations, based on Density Functional Theory (DFT) method, were performed on Calix[4]arene and Polychlorinated Dibenzo-p-dioxins (PCDDs) in gas and liquid phases for comparison purposes. The simulation results show the 1,2,3,4, 6,7,8,9-octachlorodibenzo-p-dioxin (OCDD) is quite a reactive dioxin. This paper attempts to examine the possibility of dioxin adsorption by Calix[n]arene from the environment. The interaction between Calix[4]arene and OCDD is investigated using the B3LYP method and LANL2DZ level of DFT in both gas and liquid phases. The results show that the OCDD acts as an electron acceptor and Calix[4]arene acts as an electron donor. A linear model of Quantitative Structure Activity Relationship (QSAR) has been approximated to calculate the binding affinity (BA) and induction potencies of aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD). According to this model, the calculated BA of the dioxins were found to be close to their experimental values.