Advancements in Atomically Precise Nanocluster Protected by Thiacalix[4]arene.

Coinage metal nanoclusters (NCs), comprising a few to several hundred atoms, are prized for their size-dependent properties crucial in catalysis, sensing, and biomedicine. However, their practical application is often hindered by stability and reactivity challenges. Thiacalixarene, a macrocyclic ligand, shows promise in stabilizing silver, copper, and bimetallic NCs, enhancing their structural integrity and chemical stability. This investigation delves into the unique properties of thiacalix[4]arene and their role in bolstering NC stability, catalytic efficiency, and sensing capabilities. The current challenges and future prospects are critically evaluated, underscoring the transformative impact of thiacalix[4]arene in nanoscience. This review aims to broaden the utilization of atomically precise coinage metal NCs, unlocking new avenues across scientific and industrial applications.

Controllable Assemblies of Au NPs/P5A for Enhanced Catalytic Reduction of 4-Nitrophenol.

Efficient catalytic reduction of 4-nitrophenol (4-NP) is one focus of industry and practical engineering, because 4-NP is one of the most important sources of pollution of the ecological environment and human health. Here, coassembled hybrid composites of pillar[5]arene (P5A) and gold nanoparticles (Au NPs) were successfully developed by a one-step synthetic method as a type of water-insoluble catalyst for the reduction of 4-NP. The geometric and topological structures, as well as physiochemical properties of Au NPs/P5A composite catalyst, were fully characterized and analyzed through various tests such as transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR), indicating that Au NPs were well dispersed on the surface of the two-dimensional film of assembled P5A. The influence factors of the catalytic reduction of 4-NP were further investigated and discussed, confirming that the content of Au NPs and the concentration of 4-NP were very significant during the catalysis. The catalytic reaction was carried out at the catalyst concentration of 100 mg·L-1 and an initial 4-NP concentration of 90 mg·L-1 under 30 °C. The calculated reaction rate constant was 0.3959 min-1 and the reduction rate of 4-NP was more than 95% in 20 min. In addition, the as-prepared catalyst can maintain a high catalytic efficiency after five cycles. Thus, the easily recyclable composite catalyst with poor aqueous solution can exhibit prospective application to the treatment of 4-NP in water.

Biomolecular Interactions and Anticancer Mechanisms of Ru(II)-Arene Complexes of Cinnamaldehyde-Derived Thiosemicarbazone Ligands: Analysis Combining In Silico and In Vitro Approaches.

Our study focuses on synthesizing and exploring the potential of three N-(4) substituted thiosemicarbazones derived from cinnamic aldehyde, alongside their Ru(II)-(η6 -p-cymene)/(η6-benzene) complexes. The synthesized compounds were comprehensively characterized using a range of analytical techniques, including FT-IR, UV-visible spectroscopy, NMR (1H, 13C), and HRMS. We investigated their electronic and physicochemical properties via density functional theory (DFT). X-ray crystal structures validated structural differences identified by DFT. Molecular docking predicted promising bioactivities, supported by experimental observations. Notably, docking with EGFR suggested an inhibitory potential against this cancer-related protein. Spectroscopic titrations revealed significant DNA/BSA binding affinities, particularly with DNA intercalation and BSA hydrophobic interactions. RuPCAM displayed the strongest binding affinity with DNA (Kb = 6.23 × 107 M-1) and BSA (Kb = 9.75 × 105 M-1). Assessed the cytotoxicity of the complexes on cervical cancer cells (HeLa), and breast cancer cells (MCF-7 and MDA-MB 231), revealing remarkable potency. Additionally, selectivity was assessed by examining MCF-10a normal cell lines. The active complexes were found to trigger apoptosis, a vital cellular process crucial for evaluating their potential as anticancer agents utilizing staining assays and flow cytometry analysis. Intriguingly, complexation with Ru(II)-arene precursors significantly amplified the bioactivity of thiosemicarbazones, unveiling promising avenues toward the creation of powerful anticancer agents.

Lighting Up Bispyrene-Functionalized Chiral Molecular Muscles with Switchable Circularly Polarized Excimer Emissions.

Aiming at the further extension of the application scope of traditional molecular muscles, a novel bispyrene-functionalized chiral molecular [c2]daisy chain was designed and synthesized. Taking advantage of the unique dimeric interlocked structure of molecular [c2]daisy chain, the resultant chiral molecular muscle emits strong circularly polarized luminescence (CPL) attributed to the pyrene excimer with a high dissymmetry factor (glum) value of 0.010. More importantly, along with the solvent- or anion- induced motions of the chiral molecular muscle, the precise regulation of the pyrene stacking within its skeleton results in the switching towards either "inversed" state with sign inversion and larger glum values or "down" state with maintained handedness and smaller glum values, making it a novel multistate CPL switch. As the first example of chiral molecular muscle-based CPL switch, this proof-of-concept study not only successfully widens the application scopes of molecular muscles, but also provides a promising platform for the construction of novel smart chiral luminescent materials for practical applications.

Facile Method to Obtain Functionalised η6-Bound Arenes in Ru(II) and Os(II) Half-Sandwich Complexes.

Half-sandwich Ru(II)- and Os(II)-arene complexes have great potential for catalytic and biological applications. The possibility of fine-tuning their chemical reactivity by including modifications in the ligands around the metal adds to their many advantages. However, structural modifications at the n6-bound arene have had significant synthetic limitations, particularly in the design of Os(II)-tethered complexes. For the first time, we have employed a practical C(sp3)-C(sp2) coupling to obtain 28 new Ru(II) and Os(II) η6-arene half-sandwich complexes with a wide variety of arene functionalities, including those that enable the formation of tether rings, such as quinoline and coumarin. The introduction of novel functional groups at the arene in Ru(II)- and Os(II) half-sandwich complexes can broaden the synthetic scope of this type of organometallic complexes, and help to take full advantage of their structural diversity, especially in intracellular catalysis.

Bispillar[5]arene-Based Slide-Ring Polyrotaxanation Enables Enhanced Toughness, Recyclability, Impact, and Puncture Resistance of Polyisoprene Elastomers.

A series of slide-ring polyrotaxanes (SRPs) have been constructed by the solvent-free blending of a ditopic pillar[5]arene (DP5A) and polyisoprene (PIP) after thermal annealing. Solid-state 13C NMR experiments supported the fact that the pillar[5]arene rings of DP5A were threaded by PIP chains to afford physically interlocked networks. Tensile tests revealed that 1% of DP5A can improve the elongation at break from 50 to 239%, the tensile modulus from 2.1 to 3.9 MPa, and the toughness from 0.35 to 4.5 MJ/m3. Impact and puncture resistance experiments show that the DP5A-doped materials exhibit remarkable enhancement of protective and impalement-resistant performance. The samples can be also recycled repeatedly due to their physical crosslinking nature. The important stress delocalization effects have been attributed to the pulley effect of DP5A in the SRP materials, which represents a supramolecular approach for improving the performance of PIP elastomers.

ß-Cyclodextrin/calix[4]arene hybrid porous organic polymer membrane for synergistic extraction of fluorescent whitening agents migrating from food contact materials.

Acurate and sensitive determination of hazards from food contact materials is important to monitor food safety. It is necessary to excavate efficient adsorbent for simultaneous recognition and adsorption of food hazards of trace level for sample preparation. In this work, ß-cyclodextrin and calix[4]arene were employed as hybrid functional monomers to prepare macrocyclic porous organic polymer (ß-CD-CX4 POP). It was proved that the supramolecular cavities of ß-CD-CX4 POP could form inclusion complexes with fluorescent whitening agents (FWAs) through host-guest recognition, which greatly improved the adsorption performance. The hydrophobic cavities of ß-cyclodextrin and calix[4]arene of ß-CD-CX4 POP exhibited synergistic effect for simultaneous recognition of FWAs. The high-throughput enrichment of FWAs was realized by ß-CD-CX4 POP membranes coupled with a multiple-channel syringe pump. Based on membrane-based solid-phase extraction combined with UHPLC-MS/MS, a sensitive analytical method was established to determine six FWAs. The LODs was in range of 3-50 ng/L with the linear range of 0.02-100 µg/L. The developed method was used to quantify FWAs in bread wrapper and bread, and the spiked recoveries ranged from 78.1%-119% with RSD of 2.3%-9.7%. This work indicated that ß-CD-CX4 POP was promising for the simultaneous recognition and adsorption of FWAs migrating from food contact materials.

Photocatalytic Direct para-selective C-H Amination of Benzyl Alcohols: Selectivity Independent of Side Substituents.

Aminoarenes are important molecules for broad applications in nearly all modern industries that involve chemicals. Direct and site-selective C-H bond amination of arenes provides the most efficient and convenient method to prepare aminoarenes. A main challenge is to selectively install the amino group (or other functional groups) to the distal para-carbon of arenes (especially multi-substituted arenes) during the C-H bond functionalization events. Herein, we address this problem by designing a new strategy via a sequential radical dearomatization/radical amination/rearomatization process for para-selective amination of benzyl alcohols. The para-selectivity of our reaction is completely independent of the electronic and steric properties of the other substituents of the arene substrates. Aminoarenes with many substituents (up to full substitution) and diverse substitution patterns, including those difficult to synthesize previously, could be readily prepared using our protocols. Further exploration of the current strategy shall lead to other challenging C-H functionalization of arenes.

Propanediamine modified pillar[5]arene: A novel stationary phase for the high selectivity separation of versatile analytes.

The unique properties of pillar[5]arene, including hydrophobic cavities, π-π conjugated and easy modification, make it a promising candidate as stationary phase for HPLC. Herein, we fabricated a novel propanediamine modified pillar[5]arene bonded silica as the stationary phase (PDA-BP5S) for reversed-phase liquid chromatography (RPLC). Benefiting from the significant hydrophobicity, π-π conjugative, p-π effect, and hydrogen bonding, the PDA-BP5S packed column showed high separation performance of versatile analytes involving polycyclic aromatic hydrocarbons, alkyl benzenes, phenols, arylamine, phenylethane/styrene/ phenylacetylene, toluene/m-xylene/mesitylene, halobenzenes, benzenediol and nitrophenol isomers. Especially, the separation of halobenzenes appeared to be controlled by both the size of the halogen substituents and the strength of the noncovalent bonding interactions, which was further confirmed by molecular dynamics simulation. The satisfactory separation and repeatability revealed the promising prospects of amine-pillar[5]arene-based stationary phase for RPLC.

Supramolecular Exchange Reaction in the Cavity of Naphthalene diimides Extended-Pillar[6]arene.

A new naphthalene diimides extended-pillar[6]arene 1 with a large cavity and rich host-guest complexation properties was synthesized in high yield. It can not only form 1:2 complexes with large size polycyclic aromatic hydrocarbons but also form 1:1:1 ternary complex with perylene and 2,7-diazapyrenium. Moreover, the supramolecular exchange reaction from a 1:2 host-guest complex 1•(G3)2 formed by 1 and perylene to a 1:1:1 ternary complex 1•G3•G5 formed by 1 with perylene and 2,7-diazapyrenium salt was also investigated by 1H NMR experiments as well as theoretically calculations.

Six-Cyclic Crown Ether-Type Pillar[5]Arene: Enhanced Binding Ability to Bispyridinium Derivatives.

A six-cyclic crown ether-type pillar[5]arene was synthesized, and the five ethylene oxide loops were located outside the cavity and not affected by temperature changes which was confirmed by variable-temperature NMR experiment in DMSO-d6 and CDCl3 and 2D 1H-1H NOESY experiment in CDCl3. The six-cyclic pillar[5]-crown also showed greater binding ability of host-guest with bis(pyridinium) derivatives than conventional alkoxy pillar[5]arenes that illustrated through 1H NMR titration spectroscopic experiment in acetone-d6/CDCl3 (1 : 1) and UV-vis titration experiments in CHCl3 at room temperature. The five benzocrown ethers at the periphery were able to bind metal cations by 1H NMR titration spectroscopic experiment in CD2Cl2/methanol-d4(9 : 1).

Efficient Adsorption and Elimination of Tm3+ for Enhanced Seed Germination Using Pillar[5]Arene Polymer.

While rare earth elements (REEs) are essential for modern technology, their production methods raise concerns for agriculture. Researchers are now exploring ways to control and recycle REEs pollution, aiming to minimize agricultural impacts and potentially even develop methods to utilize these elements for improved crop yields. Regarding this issue, a new type of pillar[5]arene polymer (Pol-P[5]-BTZP) has been designed and synthesized by click reaction to enhance the efficiency of adsorption and recovery of rare earth metals. This polymer incorporates the unique structure of 2,6-di-1,2,3-triazolyl-pyridine. The results of various analyses revealed that Pol-P[5]-BTZP exhibits excellent thermal stability, a high specific surface area, and well-distributed networks of micropores and mesoporous structures. The adsorption capacity of Pol-P[5]-BTZP for Tm3+, a representative REE, was evaluated using the Langmuir and Freundlich isothermal adsorption models with a maximum adsorption capacity (Qmax) of 127.71 mg/g. Furthermore, the versatility of Pol-P[5]-BTZP in adsorption and recovering various REEs was tested. In addition to its adsorption capabilities, the potential of Pol-P[5]-BTZP for rare earth recovery and reuse was assessed through experiments on the impact of Tm3+ and La3+ on seed germination. These experiments demonstrated the wide-ranging applicability of Pol-P[5]-BTZP in recovering and reusing REEs for green agriculture.

Detecting Pb2+ in aqueous environment and live cells by amphiphilic pillar[5]arene-assembled supramolecular sensor based on host-guest charge transfer mechanism.

Water-soluble fluorescent chemosensors for lead ion are highly desirable in environmental detection and bioimagery. Based on a water-soluble pillar[5]arene WP5 and imidazolium terminal functionalized 2,2'-bibenzimidazole derivative BIHB, we report a host-guest charge transfer assembly BIHB-2WP5 for sensitive and selective detection of Pb2+ in pure aqueous media. As a result of its high electron-rich cavity, WP5 can bind electron-deficiency guest BIHB with various host/guest stoichiometry to easily tune the microtopography of assembly from nanoparticle to nanocube. In view of the good biocompatibility and sensitivity, the supramolecular assembly BIHB-2WP5 was used as a fluorescent probe for the detection of Pb2+ in living cells and a smartphone Pb2+ detection device was constructed for the in situ test.

NMR analysis, cytotoxic activity and theoretical study of a complex between SRPIN340 and p-sulfonic acid calix[6]arene.

Aim: This study aimed to enhance the aqueous dissolution of SRPK inhibitor N-(2-(piperidin-1-yl)-5-(trifluoromethyl)phenyl)isonicotinamide (SRPIN340).Materials & Methods: A complex with p-sulfonic calix[6]arene (Host) and SRPIN340 (Guest) was prepared, studied via 1H nuclear magnetic resonance (NMR) and theoretical calculations and biologically evaluated on cancer cell lines.Results & conclusion: The 1:1 host (H)/guest (G) complex significantly enhanced the aqueous dissolution of SRPIN340, achieving 64.8% water solubility as determined by 1H NMR quantification analysis. The H/G complex reduced cell viability by 75% for HL60, ∼50% for Nalm6 and Jurkat, and ∼30% for B16F10 cells. It exhibited greater cytotoxicity than free SRPIN340 against Jurkat and B16F10 cells. Theoretical studies indicated hydrogen bond stabilization of the complex, suggesting broader applicability of SRPIN340 across diverse biological systems.

[Box: see text].

Host-Guest Cocrystallization of Phenanthrene[2]arene Macrocycles Facilitating Structure Determination of Liquid Organic Molecules.

Single-crystal X-ray diffraction analysis has emerged as the most reliable method for determining the structures of organic molecules. However, numerous analytes, such as liquid organic molecules, pose challenges in crystallization, making their structures directly elusive via X-ray crystallography methods. Herein, we introduced the rapid cocrystallization of a macrocycle named phenanthrene[2]arene (PTA, host) with 15 liquid organic molecules (guests). The guest liquid organic molecules were successively cocrystallized with the aid of the PTA host. Moreover, the chemical structures of the liquid organic molecules could be determined through single-crystal X-ray diffraction analysis. PTA exhibited high adaptivity and was capable of encapsulating liquid organic molecules without forming covalent bonds or strong directional interactions. The results revealed that the adaptive crystals of PTA exhibited excellent cocrystallization capacity. Weak noncovalent interactions between the host and guest molecules were crucial for organizing the guests in an ordered pattern.

Dual fluorescence response of calix[4]arene-1,8-naphthalimide derivatives towards Hg(II) /Cr(VI) and their antimicrobial studies of transparent biofilms with hyaluronic acid.

In this study, 4-sulfo-1,8-naphthalimide calixarene of derivatives were prepared (3 and 4) then transparent biofilms of the Ag salts of these compounds were formed in the presence of hyaluronic acid (HA), and antimicrobial properties were investigated. In chemosensor studies, the sensing ability behavior of 3 and 4 towards some cations and anions was investigated by fluorescence spectroscopy. It was observed that the prepared chemosensors show selectivity towards Hg(II) and Cr(VI). Ligand-ion interaction occurs according to the photo-induced electron transfer (PET) mechanism. The stoichiometric ratio was calculated by using Stern-Volmer plot method and binding constant Ksv values were found as 5.2 × 107 M-1 and 5.5 × 107 M-1 for 3-Hg(II) and 4-Hg(II) complexes, respectively and 4.0 × 107 M-1 and 4.3 × 107 M-1 for 3-Cr(VI) and 4-Cr(VI) complexes. The detection limits of the complexes of 3-Hg(II) and 4-Hg(II) are 6.35 × 10-12and 6.81 × 10-12, while those of 3-Cr(VI) and 4-Cr(VI) are 1.41 × 10- 11and 8.37 × 10-12, respectively. As a result of the antimicrobial test performed with these compounds, it was observed that the most effective material was HA-3Ag, which showed a significant antibacterial effect against Sarcina lutea (S. lutea) at a minimum inhibitory concentration (MIC) value of 0.097 mg/mL.

Sensing Volatile Pollutants with Spin-Coated Films Made of Pillar[5]arene Derivatives and Data Validation via Artificial Neural Networks.

Different types of solvents, aromatic and aliphatic, are used in many industrial sectors, and long-term exposure to these solvents can lead to many occupational diseases. Therefore, it is of great importance to detect volatile organic compounds (VOCs) using economic and ergonomic techniques. In this study, two macromolecules based on pillar[5]arene, named P[5]-1 and P[5]-2, were synthesized and applied to the detection of six different environmentally volatile pollutants in industry and laboratories. The thin films of the synthesized macrocycles were coated by using the spin coating technique on a suitable substrate under optimum conditions. All compounds and the prepared thin film surfaces were characterized by NMR, Fourier transform infrared (FT-IR), elemental analysis, atomic force microscopy (AFM), scanning electron microscopy (SEM), and contact angle measurements. All vapor sensing measurements were performed via the surface plasmon resonance (SPR) optical technique, and the responses of the P[5]-1 and P[5]-2 thin-film sensors were calculated with ΔI/Io × 100. The responses of the P[5]-1 and P[5]-2 thin-film sensors to dichloromethane vapor were determined to be 7.17 and 4.11, respectively, while the responses to chloroform vapor were calculated to be 5.24 and 2.8, respectively. As a result, these thin-film sensors showed a higher response to dichloromethane and chloroform vapors than to other harmful vapors. The SPR kinetic data for vapors validated that a nonlinear autoregressive neural network was performed with exogenous input for the best molecular modeling by using normalized reflected light intensity values. It can be clearly seen from the correlation coefficient values that the nonlinear autoregressive with exogenous input artificial neural network (NARX-ANN) model for dichloromethane converged more successfully to the experimental data compared to other gases. The correlation coefficient values of the dichloromethane modeling results were approximately 0.99 and 0.98 for P[5]-1 and P[5]-2 thin-film sensors, respectively.

Phenyl-Extended Resorcin[4]arenes: Synthesis and Highly Efficient Iodine Adsorption.

The continuous exploration of new analogs of calixarenes and pillararenes unlocks infinite opportunities in supramolecular chemistry and materials. In this work, we introduce a new class of macrocycle, phenyl-extended resorcin[4]arenes (ExR4), a unique and innovative design that incorporates unsubstituted phenylene moieties into the resorcin[4]arene scaffold. Single-crystal analysis reveals a chair-like conformation for per-methylated ExR4 (Me-ExR4) and a twisted "Figure-of-eight" shaped conformation for per-hydroxylated ExR4 (OH-ExR4). Notably, OH-ExR4 demonstrates exceptional adsorption capability toward I3 - ions in an aqueous solution, with a rapid kinetic rate of 1.18×10-2 g ⋅ mg-1 ⋅ min-1. Furthermore, OH-ExR4 shows excellent recyclability and potential as a stationary phase in column setups. The discovery of ExR4 opens up new avenues for constructing new macrocycles and inspires further research in functional adsorption materials for water pollutant removal.

Dual pH and Ca2+-Responsive PEG-Modified Pillar[5]arene-Based Supramolecular Nanodrug Delivery System: Excellent Cargo Encapsulation and Minimal Drug Toxicity.

Chemotherapy is one of the most employed strategies in clinical treatment of cancer. However, reducing medication adverse effects and improving the biological activity remains a significant issue for chemotherapy. We developed a pH and Ca2+-responsive pillar[5]arene-based supramolecular nanodrug delivery system (NDDS) WP5⊃EV@DOX to address the aforementioned challenges. The formation of this NDDS began with the spontaneous formation of supramolecular nanodrug carrier WP5⊃EV in water from PEG-modified pillar[5]arene and the bipyridilium salt derivative EV through simple host-guest interaction. Then the antitumor drug doxorubicin DOX was efficiently loaded with a high encapsulation rate of 84.6 %. Cytotoxicity results indicated that the constructed nanoplatform not only reduced DOX toxicity and side effects on normal cell (293T), but also significantly enhanced the antitumor activity on cancer cell (HepG2). Moreover, in vivo experiments showed that WP5⊃EV@DOX had a longer half-life and higher bioavailability in the blood of mice compared to the nake drug DOX, with increases to 212 % and 179 %, respectively. Therefore, WP5⊃EV@DOX has great potential in tumor therapy and provides a new idea for host-guest drug delivery system.

Synthesis and crystal structures of 5,17-di-bromo-26,28-dihy-droxy-25,27-dipropynyloxycalix[4]arene, 5,17-di-bromo-26,28-dipropoxy-25,27-dipropynyloxycalix[4]arene and 25,27-bis-(2-azido-eth-oxy)-5,17-di-bromo-26,28-di-hydroxy-calix[4]arene.

The calixarenes, 5,17-di-bromo-26,28-dihy-droxy-25,27-dipropynyloxycalix[4]arene (C34H26Br2O4, 1), 5,17-di-bromo-26,28-dipropoxy-25,27-dipropynyloxycalix[4]arene (C40H38Br2O4, 2) and 25,27-bis-(2-azido-eth-oxy)-5,17-di-bromo-26,28-di-hydroxy-calix[4]arene (C32H28Br2N6O4, 3) possess a pinched cone mol-ecular shape for 1 and 3, and a 1,3-alternate shape for compound 2. In calixarenes 1 and 3, the cone conformations are additionally stabilized by intra-molecular O-H⋯O hydrogen bonds, while in calixarene 2 intra-molecular Br⋯Br inter-actions consolidate the 1,3-alternate mol-ecular conformation. The dense crystal packing of the cone dialkyne 1 is a consequence of π-π, C-H⋯π and C-H⋯O inter-actions. In the crystal of the diazide 3, there are large channels extending parallel to the c axis, which are filled by highly disordered CH2Cl2 solvent mol-ecules. Their contribution to the intensity data was removed by the SQUEEZE procedure that showed an accessible void volume of 585 Å3 where there is room for 4.5 CH2Cl2 solvent mol-ecules per unit cell. Rigid mol-ecules of the 1,3-alternate calixarene 2 form a columnar head-to-tail packing parallel to [010] via van der Waals inter-actions, and the resulting columns are held together by weak C-H⋯π contacts.