Chrysin-loaded calixarene-cyclodextrin ternary drug delivery system inhibits TGF-ß and galectin-1 mediated pathways in diabetic liver fibrosis.

This study investigated the efficacy of a new chrysin-loaded calixarene-cyclodextrin ternary drug delivery system (DDS) in reversing liver fibrosis in a mouse model of chronic diabetes. The system was designed to enhance the solubility and bioavailability of chrysin (CHR) and calixarene 0118 (OTX008). Adult male CD1 mice received streptozotocin (STZ) injections to induce diabetes. After 20 weeks, they underwent intraperitoneal treatments twice weekly for a two-week period. Histological analyses revealed that long-term hyperglycaemia increased liver fibrosis and altered hepatic ultrastructure, characterized by lipid accumulation, hepatic stellate cell activation, and collagen deposition. The treatment with the chrysin-loaded DDS restored liver structure closely to normal levels, as opposed to the minimal impact observed with sulfobutylated ß-cyclodextrin (SBECD) alone. The treatment significantly decreased serum activities of alanine /aspartate transaminases and reduced the gene expression of collagen type I (Col-I). It also modulated the transforming growth factor beta 1 (TGF-ß1)/Smad signalling pathway, inhibiting the activation and proliferation of hepatic stellate cells. The treatment led to a downregulation of the TGF-ß1 gene and its receptors TGFßR1 and TGFßR2, together with a decrease in Smad 2 and 3 mRNA levels. Conversely, Smad 7 mRNA expression was increased by the DDS. Furthermore, it downregulated galectin-1 (Gal-1) gene and protein levels, which correlated with fibrotic markers. In conclusion, the chrysin-loaded calixarene-cyclodextrin ternary DDS presents a promising therapeutic approach for diabetic liver fibrosis, effectively targeting fibrotic pathways and restoring hepatic function and structure.

Antibody-Calixarene Drug Conjugate: A General Drug Delivery Platform for Tumor-Targeted Therapy.

Antibody-drug conjugates (ADCs), which combine the precise targeting capabilities of antibodies with the powerful cytotoxicity of small-molecule drugs, have evolved into a promising approach for tumor treatment. However, the traditional covalent coupling method requires the design of a specific linker tailored to the properties of the small-molecule drugs, which greatly limits the development of ADCs and the range of drugs that can be used. Herein, a novel type of antibody-calixarene drug conjugates (ACDCs) that function similarly to ADCs by delivering drugs to their targets using antibodies but without the requirement of covalent conjugation of the drugs with antibodies is presented. By replacement of conventional linkers with supramolecular linkers, the ACDCs can load various chemotherapeutic drugs through host-guest interactions. Furthermore, ACDCs are readily reduced upon reaching the hypoxic microenvironment, resulting in rapid release of the drugs. With this precise drug encapsulation and controlled release mechanism, ACDCs deliver drugs to tumor tissues effectively and achieve a significantly enhanced antitumor effect. Considering that the ACDCs can be easily prepared by combining antibody-calixarene conjugates derived from tumor-targeting antibodies with various small-molecule drugs, ACDCs may provide a promising platform technology to accelerate ADC development and thus improve the therapeutic efficacy of chemotherapy.

Post-Synthetic Modification of Calix[4]arene Framework by Iridium-Mediated Alkyne Insertion into an Inert C-C Bond: A Novel Strategy for Unsymmetrical Macrocycles.

As a novel synthetic method for unsymmetrical macrocycles, we herein developed a post-synthetic modification of calix[4]arenes by insertion of a terminal alkyne into an inert C(methylene)-C(aryl) bond of the macrocyclic framework. In this transformation, C-iridated calix[4]arenes, readily synthesized through C-H bond activation of the parent calix[4]arene, undergoes C(methylene)-C(aryl) bond cleavage followed by insertion of an alkyne to provide a ring-expanded calix[4]arene complex. Removal of the iridium metal from the resulting complex was readily accomplished by a simple treatment with an acid. The developed sequential method affords novel unsymmetrical, monofunctionalized macrocyclic compounds via 3 steps from the parent calix[4]arene in good yield. The unique unsymmetrical structures of the alkyne-inserted macrocycles were evaluated by X-ray single crystal analyses. On the basis of theoretical calculations, we propose a reaction mechanism involving an uncommon C-C bond cleavage step through δ-carbon elimination for the ring enlargement process.

Analyzing urinary hippuric acid as a metabolic health biomarker through a supramolecular architecture.

The prevalence of metabolic disorders has been found to increase concomitantly with alternations in habitual diet and lifestyle, indicating the importance of metabolic health monitoring for early warning of high-risk status and suggesting effective intervention strategies. Hippuric acid (HA), as one of the most abundant metabolites from the gut microbiota, holds potential as a regulator of metabolic health. Accordingly, it is imperative to establish an efficient, sensitive, and affordable method for large-scale population monitoring, revealing the association between HA level and metabolic disorders. Upon systematic screening of macrocycle•dye reporter pair, a supramolecular architecture (guanidinomethyl-modified calix[5]arene, GMC5A) was employed to sense urinary HA by employing fluorescein (Fl), whose complexation behavior was demonstrated by theoretical calculations, accomplishing quantification of HA in urine from 249 volunteers in the range of 0.10 mM and 10.93 mM. Excitedly, by restricted cubic spline, urinary HA concentration was found to have a significantly negative correlation with the risk of metabolic disorders when it exceeded 0.76 mM, suggesting the importance of dietary habits, especially the consumption of fruits, coffee, and tea, which was unveiled from a simple questionnaire survey. In this study, we accomplished a high throughput and sensitive detection of urinary HA based on supramolecular sensing with the GMC5A•Fl reporter pair, which sheds light on the rapid quantification of urinary HA as an indicator of metabolic health status and early intervention by balancing the daily diet.

Calixarene-Based Supramolecular Sensor Array for Pesticide Discrimination.

The identification and detection of pesticides is crucial to protecting both the environment and human health. However, it can be challenging to conveniently and rapidly differentiate between different types of pesticides. We developed a supramolecular fluorescent sensor array, in which calixarenes with broad-spectrum encapsulation capacity served as recognition receptors. The sensor array exhibits distinct fluorescence change patterns for seven tested pesticides, encompassing herbicides, insecticides, and fungicides. With a reaction time of just three minutes, the sensor array proves to be a rapid and efficient tool for the discrimination of pesticides. Furthermore, this supramolecular sensing approach can be easily extended to enable real-time and on-site visual detection of varying concentrations of imazalil using a smartphone with a color scanning application. This work not only provides a simple and effective method for pesticide identification and quantification, but also offers a versatile and advantageous platform for the recognition of other analytes in relevant fields.

Identification of Potential Drug Targets of Calix[4]arene by Reverse Docking.

Calixarenes are displaying great potential for the development of new drug delivery systems, diagnostic imaging, biosensing devices and inhibitors of biological processes. In particular, calixarene derivatives are able to interact with many different enzymes and function as inhibitors. By screening of the potential drug target database (PDTD) with a reverse docking procedure, we identify and discuss a selection of 100 proteins that interact strongly with calix[4]arene. We also discover that leucine (23.5 %), isoleucine (11.3 %), phenylalanines (11.3 %) and valine (9.5 %) are the most frequent binding residues followed by hydrophobic cysteines and methionines and aromatic histidines, tyrosines and tryptophanes. Top binders are peroxisome proliferator-activated receptors that already are targeted by commercial drugs, demonstrating the practical interest in calix[4]arene. Nuclear receptors, potassium channel, several carrier proteins, a variety of cancer-related proteins and viral proteins are prominent in the list. It is concluded that calix[4]arene, which is characterized by facile access, well-defined conformational characteristics, and ease of functionalization at both the lower and higher rims, could be a potential lead compound for the development of enzyme inhibitors and theranostic platforms.

Synthesis of Calix[4]arene-Based Porous Organic Cages and Their Gas Adsorption.

Two crystalline large-sized porous organic cages (POCs) based on conical calix[4]arene (C4A) were designed and synthesized. The four-jaw C4A unit tends to follow the face-directed self-assembly law with the planar triangular building blocks such as tris(4-aminophenyl)amine (TAPA) or 1,3,5-tris(4-aminophenyl)benzene (TAPB) to generate a predictable cage with a stoichiometry of [6+8]. The formation of the large cages is confirmed through their relative molecular mass measured using MALDI-TOF/TOF spectra. The protonated molecular ion peaks of C4A-TAPA and C4A-TAPB were observed at m/z 5109.0 (calculated for C336H240O24N32: m/z 5109.7) and m/z 5594.2 (calculated for C384H264O24N24: m/z 5598.4). C4A-POCs exhibit I-type N2 adsorption-desorption isotherms with the BET surface areas of 1444.9 m2 ⋅ g-1 and 1014.6 m2 ⋅ g-1. The CO2 uptakes at 273 K are 62.1 cm3 ⋅ g-1 and 52.4 cm3 ⋅ g-1 at a pressure of 100 KPa. The saturated iodine vapor static uptakes at 348 K are 3.9 g ⋅ g-1 and 3.5 g ⋅ g-1. The adsorption capacity of C4A-TAPA for SO2 reaches to 124.4 cm3 ⋅ g-1 at 298 K and 1.3 bar. Additionally, the adsorption capacities of C4A-TAPA for C2H2, C2H4, and C2H6 were evaluated.

Active targeting tumor therapy using host-guest drug delivery system based on biotin functionalized azocalix[4]arene.

Host-guest drug delivery systems (HGDDSs) provided a facile method for incorporating biomedical functions, including efficient drug-loading, passive targeting, and controlled drug release. However, developing HGDDSs with active targeting is hindered by the difficult functionalization of popular macrocycles. Herein, we report an active targeting HGDDS based on biotin-modified sulfonated azocalix[4]arene (Biotin-SAC4A) to efficiently deliver drug into cancer cells for improving anti-tumor effect. Biotin-SAC4A was synthesized by amide condensation and azo coupling. Biotin-SAC4A demonstrated hypoxia responsive targeting and active targeting through azo and biotin groups, respectively. DOX@Biotin-SAC4A, which was prepared by loading doxorubicin (DOX) in Biotin-SAC4A, was evaluated for tumor targeting and therapy in vitro and in vivo. DOX@Biotin-SAC4A formulation effectively killed cancer cells in vitro and more efficiently delivered DOX to the lesion than the similar formulation without active targeting. Therefore, DOX@Biotin-SAC4A significantly improved the in vivo anti-tumor effect of free DOX. The facilely prepared Biotin-SAC4A offers strong DOX complexation, active targeting, and hypoxia-triggered release, providing a favorable host for effective breast cancer chemotherapy in HGDDSs. Moreover, Biotin-SAC4A also has potential to deliver agents for other therapeutic modalities and diseases.

Upper Rim-Bridged Calix[4]arenes via Cyclization of meta Alkynyl Intermediates with Diphenyl Diselenide.

A Sonogashira coupling of meta-iodocalix[4]arene with various terminal acetylenes confirmed that the meta position of calixarene is well addressable, and that both thermal and microwave protocols led to good yields of alkynylcalixarenes. Alkynes thus obtained were subjected to the ferric chloride and diphenyl diselenide-promoted electrophilic closure. It turns out that the calix[4]arenes give completely different bridging products than those described for the non-macrocyclic starting compounds. This can be demonstrated not only by the isolation of products with a six-membered ring (6-exo-dig), but mainly by the smooth formation of the 5-endo-dig cyclization, which has never been observed in the aliphatic series. An attempt at electrocyclization led to a high yield of the 1,2-diketone (oxidation of the starting alkyne), again in contrast to the reaction described for the acyclic derivatives. The structures of the unexpected products were unequivocally established by X-ray analysis and clearly demonstrate how the preorganized macrocyclic skeleton favors a completely different regioselectivity of cyclization reactions compared to common aliphatic compounds.

Fabrication and investigation of a pentamerous composite based on calix[4]arene functionalized graphene oxide grafted with silk fibroin, cobalt ferrite, and alginate.

This paper presents a new scaffold made from graphene oxide nanosheets, calix[4]arene supramolecules, silk fibroin proteins, cobalt ferrite nanoparticles, and alginate hydrogel (GO-CX[4]/SF/CoFe2O4/Alg). After preparing the composite, we conducted various analyses to examine its structure. These analyses included FTIR, XRD, SEM, EDS, VSM, DLS, and zeta potential tests. Additionally, we performed tests to evaluate the swelling ratio, rheological properties, and compressive mechanical strength of the material. The biological capability of the composite was tested through biocompatiblity, anticancer, hemolysis, antibacterial anti-biofilm assays. Besides, the rheological properties and swelling behaviour of the composite were studied. The results showed that the scaffold is biocompatible with Hu02 cells and the cell viability percentages of 85.23 %, 82.78 %, and 80.18 % for were acquired for 24, 48, and 72 h, respectively. In contrast, the cell viability percentage of BT549 cancer cells were obtained 65.79 %, 60.45 % and 58.16 % for same period which confirmed notable anticancer activity of the product composite. Moreover, a significant antibacterial growth inhibition against E. coli and S. aureus species highlights its potential as an effective antibacterial agent. Furthermore, the observed minimal hemolytic effect (6.56 %) and strong inhibition of P. aeruginosa biofilm formation with a low OD value (0.24) indicate notable hemocompatibility and antibacterial activity.

Novel mitochondrial and DNA damaging fluorescent Calix[4]arenes bearing isatin groups as aromatase inhibitors: Design, synthesis and anticancer activity.

Breast cancer causes a high rate of mortality all over the world. Therefore, the present study focuses on the anticancer activity of new lower rim-functionalized calix[4]arenes integrated with isatin and the p-position of calixarenes with 1,4-dimethylpyridinium iodine against various human cancer cells such as MCF-7 and MDA-MB-231 breast cancer cell lines, as well as the PNT1A healthy epithelial cell line. It was observed that compound 6c had the lowest values in MCF-7 (8.83 µM) and MDA-MB-231 (3.32 µM). Cell imaging and apoptotic activity studies were performed using confocal microscopy and flow cytometry, respectively. The confocal imaging studies with 6c showed that the compound easily entered the cell, and it was observed that 6c accumulated in the mitochondria. The Comet assay test was used to detect DNA damage of compounds in cells. It was found that treated cells had abnormal tail nuclei and damaged DNA structures compared with untreated cells. In vitro human aromatase enzyme inhibition profiles showed that compound 6c had a remarkable inhibitory effect on aromatase. Compound 6c displayed a significant inhibition capacity on aromatase enzyme with the IC50 value of 0.104 ± 0.004 µM. Thus, not only the anticancer activity of the new fluorescent derivatives, which are the subject of this study, but the aromatase inhibitory profiles have also been proven.

Supramolecular Assembly Based on Calix(4)arene and Aggregation-Induced Emission Photosensitizer for Phototherapy of Drug-Resistant Bacteria and Skin Flap Transplantation.

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.

Novel An Efficient Fluorescent Probe Based on Calix[4]triazacrown-5 With Naphthalimide Group for Co2+, Cd2+ and Dopamine Detection.

A novel naphthalimide-substituted calix[4]triazacrown-5 (Nap-Calix) at cone conformation was designed and synthesized to employ as a fluorescent probe, which enables the simultaneously detection of Co2+ and Cd2+ metal ions as well as dopamine (DA). 1H-NMR, 13C-NMR, ESI-MS and elemental analysis techniques were carried out to characterize its structure. Cation binding property of Nap-Calix against various metal ions such as Ba2+, Co2+, Ni2+, Pb2+, Zn2+, and Cd2+ exhibited that the sensor selectively binds to Co2+ and Cd2+ metal ions with a remarkable affinity. Introduction of Co2+ and Cd2+ metal ions to a solution of Nap-Calix in DMF/water (1:1, v/v) resulted with a new emission band at 370 nm when excited at 283 nm. In addition, the fluorescence sensing affinity of the probe Nap-Calix against a catecholamine neurotransmitter (dopamine) was investigated in a wide range of concentration of DA (0-0.1 mmol L-1) in 50% DMF/PBS (pH = 5.0). The fluorescence intensity of Nap-Calix, with excitation/emission peaks at 283/327 nm, is highly enhanced by DA. It was also observed that Nap-Calix exhibits excellent fluorescence behavior towards DA with a very low detection limit as 0.21 µmol L-1.

A Sequential Dual Functional Supramolecular Hydrogel with Promoted Drug Release to Scavenge ROS and Stabilize HIF-1α for Myocardial Infarction Treatment.

Myocardial infarction (MI) has a characteristic inflammatory microenvironment due to the overproduction of reactive oxygen species (ROS) and causes the extraordinary deposition of collagen and thereby fibrosis. An on-demand adaptive drug releasing hydrogel is designed to modulate the inflammatory microenvironment and inhibit cardiac fibroblasts (CFs) proliferation post MI by scavenging the overproduced ROS and releasing 1,4-dihydrophenonthrolin-4-one-3-carboxylic acid (DPCA) to maintain the expression of hypoxia-inducible factor 1α (HIF-1α). DPCA is prefabricated to a prodrug linked with disulfide bond (DPCA-S-S-OH). The DPCA-S-S-OH and carboxylated calixarene (CSAC4A) are grafted onto the backbone of methacrylated hyaluronic acid (HAMA) to obtain HAMA-S-S-DPCA and HAMA-CA, respectively, which are further reacted to form a dual network hydrogel (R+ /DPCA(CA)) with covalent linking and host-guest interaction between DPCA and CSAC4A. The ROS-triggered hydrolysis of ester bond and subsequently sustaining release of DPCA from the cavity of CSAC4A jointly cause the constant expression of HIF-1α, which significantly restricts the CFs proliferation, leading to suppressed fibrosis and promoted heart repair.

New Carboxytriazolyl Amphiphilic Derivatives of Calix[4]arenes: Aggregation and Use in CuAAC Catalysis.

This work focuses on the synthesis of a new series of amphiphilic derivatives of calix[4]arenes for the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The aggregation properties of synthesized calix[4]arenes were studied using various techniques (fluorescence spectroscopy, nanoparticle tracking analysis, and dynamic light scattering). Increasing the length of the alkyl substituent led to stronger hydrophobic interactions, which increased polydispersity in solution. The zwitterionic nature of the synthesized calix[4]arenes was established using different types of dyes (Eosin Y for anionic structures and Rhodamine 6G for cationic structures). The synthesized calix[4]arenes were used as organic stabilizers for CuI. The catalytic efficiency of CuI-calix[4]arene was compared with that of the phase transfer catalyst tetrabutylammonium bromide (TBAB) and the surfactant sodium dodecyl sulfate (SDS). For all calixarenes, the selectivity in the CuAAC reaction was higher than that observed when TBAB and SDS were estimated.

A highly selective and sensitive fluorescence probe for dopamine determination based on a bisquinoline-substituted calix[4]arene carboxylic acid derivative.

Dopamine (DA) at normal levels in the human body exhibits a high potential for maintaining a proper neuron network. However, their abnormalities in humans can bring out aggressive disorders such as Schizophrenia, hypertension, Tourette's syndrome, Alzheimer's disease, bipolar depression, Parkinson's disease, drug addiction and attention-deficit hyperactivity diseases. Hence, in this study, a bis-quinoline-substituted calix[4] arene carboxylic acid derivative (Quin-Calix-CO2H) at cone conformation was developed as an effective fluorescent sensor for the detection of a catecholamine neurotransmitter (dopamine). The structure of Quin-Calix-CO2H was confirmed using 1H-NMR, 13C-NMR, ESI-MS and elemental analysis techniques. The calixarene-based fluorescent sensor (Quin-Calix-CO2H) has shown fluorescence emission at 404 nm under the excitation of 270 nm. Further, biomolecules binding property of Quin-Calix-CO2H against various biomolecules such as L-cysteine (L-Cys), α-D-glucose (D-Glu), (+)-sodium-L-ascorbate (SAA), urea (UR), L-alanine (L-Ala) and dopamine (DA) exhibited that the fluorescent sensor enables selectively and sensitively detection for DA with a remarkable affinity. The probe Quin-Calix-CO2H has shown fluorescence quenching towards DA concentration ranging from 0 to 4.0 µM with a very low limit of detection (LOD) of 88.5 nmol L-1. In addition, the binding constant and stoichiometry as well as the mechanism of quenching have been also determined from the fluorescence data.Communicated by Ramaswamy H. Sarma.

Synthetic Receptors for Early Detection and Treatment of Cancer.

Over recent decades, synthetic macrocyclic compounds have attracted interest from the scientific community due to their ability to selectively and reversibly form complexes with a huge variety of guest moieties. These molecules have been studied within a wide range of sensing and other fields. Within this review, we will give an overview of the most common synthetic macrocyclic compounds including cyclodextrins, calixarenes, calixresorcinarenes, pillarenes and cucurbiturils. These species all display the ability to form a wide range of complexes. This makes these compounds suitable in the field of cancer detection since they can bind to either cancer cell surfaces or indeed to marker compounds for a wide variety of cancers. The formation of such complexes allows sensitive and selective detection and quantification of such guests. Many of these compounds also show potential for the detection and encapsulation of environmental carcinogens. Furthermore, many anti-cancer drugs, although effective in in vitro tests, are not suitable for use directly for cancer treatment due to low solubility, inherent instability in in vivo environments or an inability to be adsorbed by or transported to the required sites for treatment. The reversible encapsulation of these species in a macrocyclic compound can greatly improve their solubility, stability and transport to required sites where they can be released for maximum therapeutic effect. Within this review, we intend to present the use of these species both in cancer sensing and treatment. The various macrocyclic compound families will be described, along with brief descriptions of their synthesis and properties, with an outline of their use in cancer detection and usage as therapeutic agents. Their use in the sensing of environmental carcinogens as well as their potential utilisation in the clean-up of some of these species will also be discussed.

α-Methylbenzylamine Functionalized Crown-Ether-Appended Calix[4]arene Phase Transfer Catalyst for Enantioselective Henry Reaction.

In this letter, we designed a highly selective α-methylbenzylamine functionalized crown-ether-appended calix[4]arene derived phase transfer catalyst for asymmetric nitroaldol reaction to provide the desired nitroaldol adducts in high yields (up to 99 % yield) with good to excellent enantioselectivities (up to 99.8 % ee).

Calix[4]arene-Derived 2D Covalent Organic Framework with an Electron Donor-Acceptor Structure: A Visible-Light-Driven Photocatalyst.

The calixarenes are ideal building blocks for constructing photocatalytic covalent organic frameworks (COFs), owing to their electron-rich and bowl-shaped π cavities that endow them with electron-donating and adsorption properties. However, the synthesis and structural confirmation of COFs based on calixarenes are still challenging due to their structural flexibility and conformational diversity. In this study, a calix[4]arene-derived 2D COF is synthesized using 5,11,17,23-tetrakis(p-formyl)-25,26,27,28-tetrahydroxycalix[4]arene (CHO-C4A) as the electron donor and 4,7-bis(4-aminophenyl)-2,1,3-benzothiadiazole (BTD) as the acceptor. The powder X-ray diffraction data and theoretical simulation of crystal structure indicate that COF-C4A-BTD exhibits high crystallinity and features a non-interpenetrating undulating 2D layered structure with AA-stacking. The density functional theory theoretical calculation, transient-state photocurrent tests, and electrochemical impedance spectroscopy confirm the intramolecular charge transfer behavior of COF-C4A-BTD with a donor-acceptor structure, leading to its superior visible-light-driven photocatalytic activity. COF-C4A-BTD exhibits a narrow band gap of 1.99 eV and a conduction band energy of -0.37 V versus normal hydrogen electrode. The appropriate energy band structure can facilitate the participation of ·O2- and h+ . COF-C4A-BTD demonstrates high efficacy in removing organic pollutants, such as bisphenol A, rhodamine B, and methylene blue, with removal rates of 66%, 85%, and 99% respectively.

Synthesis of Imidazolium Cations Linked to Para-t-Butylcalix[4]arene Frameworks and Their Use as Synthons for Nickel-NHC Complexes Tethered to Calix[4]arenes.

A series of cationic p-tert-butylcalix[4]arenes, with side-arms that are functionalized with imidazolium groups, have been synthesized in good yields. The parent tetrahydroxy para-t-butyl-calix[4]arene was dialkylated at the phenolic hydrogen atoms using α,ω-dibromo-alkanes to yield bis(mono-brominated) alkoxy-chains of variable length. The brominated side-arms in these compounds were then further alkylated with substituted imidazoles (N-methylimidazole, N-(2,4,6-trimethyl-phenyl)imidazole, or N-(2,6-di-isopropylphenyl)imidazole) to yield a series of dicationic calixarenes with two imidazolium groups tethered, via different numbers of methylene spacers (n = 2-4), to the calixarene moiety. Related tetracationic compounds, which contain four imidazolium units linked to the calix[4]arene backbone, were also prepared. In all of these compounds, the NMR data show that the calixarenes adopted a cone configuration. All molecules were characterized by NMR spectroscopy and by MS studies. Single crystal X-ray diffraction studies were attempted on many mono-crystals of these cations, but significant disorder problems, partly caused by occluded solvent in the lattice, and lack of crystallinity resulting from partial solvent loss, precluded the good resolution of most X-ray structures. Eventually, good structural data were obtained from an unusually disordered single crystal of 5a, (1,3)-Cone-5,11,17,23-tetra-t-butyl-25,27-di-hydroxy-26,28-di-[2-(N-2,6-diisopropylphenyl-imidazolium)ethoxy]calix[4]arene dibromide and its presumed structure was confirmed. The structure revealed the presence of H-bonded interactions and some evidence of π-stacking. Some of these imidazolium salts were reacted with nickelocene to form the nickel N-heterocyclic carbene (NHC) complexes 7a-7d. A bis-carbene nickel complex 8 was also isolated and its structure was established by single crystal X-ray diffraction studies. The structure was disordered and not of high quality, but the structural data corroborated the spectroscopic data.