A new thiacalix[4]arene-based metal-organic framework as an efficient electrochemical sensor for trace detection of Cd2+ and Pb2.

Heavy metal ions (HMIs) can lead to serious harm to human health and ecological environment. Thus, developing an efficient detection method for HMIs is extremely necessary. Herein, a new thiacalix[4]arene-based metal-organic framework (MOF) [Co2(L1)(TPA)2]·DMA·3CH3OH·H2O (Co-LTPA) (L1 = thiacalix[4]arene-based ligand and H2TPA = terephthalic acid) was successfully synthesized. The electrochemical detection platform (Co-LTPA/GCE) was acquired, and Co-LTPA/GCE featured ultrasensitive detection of HMIs with greatly low limits of detection (LODs) of 0.119 nM for Cd2+ and 0.279 nM for Pb2+ as well as wide linear ranges of 0.08-5.8 µM for Cd2+ and 0.01-6.0 µM for Pb2+. More importantly, the Co-LTPA/GCE sensor was employed to detect foods (milk, honey and orange juice) and water samples (tap water, lake water and drinking water) with satisfactory recoveries, proving the sensor reliability in practical applications. This work provided an example that the functional electrochemical Co-LTPA/GCE sensor was employed for Cd2+ and Pb2+ detection.

Composite of a thiacalix[4]arene-copper(I) metal-organic framework and mesoporous carbon for efficient electrochemical detection of antibiotics.

Abundant use of nitrofurantoin (NFT) and metronidazole (MTZ) antibiotics has led to excessive residues in the environments and humans, resulting in serious damage to the human body and ecosystem. Therefore, effective detection of NFT and MTZ is exceedingly necessary. In this regard, metal-organic frameworks (MOFs) are promising materials as electrochemical sensors. Herein, we synthesized a new two-dimensional thiacalix [4]arene-copper (I) MOF (Cu-TC4A-M). This MOF was mixed with mesoporous carbon (MC) to a give Cu-TC4A-M@MC composite. In addition, the sensors of Cu-TC4A-M@MC(2:1)/GCE and Cu-TC4A-M@MC(1:2)/GCE were achieved (GCE = glassy carbon electrode), and then were applied for effectively detecting NFT and MTZ, respectively. Markedly, the two sensors exhibited satisfactory linear detection range, anti-interference, reproducibility and stability. When they were utilized in the real samples, such as human serum, urine, tap water and lake water, satisfactory recoveries were attained. The relative standard deviations (RSDs) were in the range of 1.16 % âˆ¼ 1.92 % for NFT and 0.95 % âˆ¼ 2.33 % for MTZ. This work provided a new application prospect for the thiacalix [4]arene-based MOFs as promising candidate materials for NFT and MTZ detection.

Electrochemical Detection of Flutamide by the Composite of Complex Based on Thiacalix[4]arene Derivatives and Reduced Graphene Oxide.

In this paper, a thiacalix[4]arene complex [Zn2(TIT4A)L2]·4DMF·2CH3OH (H2L = 4,4'-oxybisbenzoic acid) (Zn-TIT4A-L) was synthesized by a solvothermal method. The composites were prepared by combining Zn-TIT4A-L with reduced graphene oxide (RGO), mesoporous carbon (MC), and multi-walled carbon nanotubes (MWCNTs), respectively. Three representative composites are Zn-TIT4A-L@RGO(1:1), Zn-TIT4A-L@MC(1:2), and Zn-TIT4A-L@MWCNT(1:2). X-ray diffraction and scanning electron microscopy characterized their structures and morphologies. The results showed that three composites were successfully prepared, and the crystals of the complex remained in the composites. The electrochemical properties of the composites were characterized by electrochemical impedance spectroscopy and cyclic voltammetry. The results indicated that they had good electrocatalytic activity and conductivity. Among them, Zn-TIT4A-L@RGO(1:1) had the best performance and was used for the quantitative detection of flutamide (FTA). The linear range of detection is 0.1-200 µM, and the limit of detection is 0.015 µM. At the same time, the sensor also had good reproducibility, anti-interference, and stability. The sensor was also used for the detection of FTA in lake water, human urine, and serum with a satisfactory recovery rate. The possible mechanism of electrochemical detection of FTA was also discussed.

Thiacalix[4]arene-based metal-organic framework/reduced graphene oxide composite for electrochemical detection of chlorogenic acid.

A novel metal-organic framework [Co2LCl4]·2DMF (Co-L) based on thiacalix[4]arene derivative was synthesized using the solvothermal method. Then Co-L was respectively mixed with reduced graphene oxide (RGO), multi-walled carbon nanotubes (MWCNT) and mesoporous carbon (MC) to prepare corresponding composite materials. PXRD, SEM and N2 adsorption-desorption illustrated that composite materials have been successfully prepared. After optimizing experimental conditions for detecting chlorogenic acid (CGA), the Co-L@RGO(1:1) composite material showed the optimal electrocatalytic activity for CGA, which may be because RGO possessed large specific surface area and hydroxyl and carboxyl groups that could form hydrogen-bonding with the oxide of CGA. Benefiting from the synergetic effect of Co-L and RGO, the glassy carbon electrode modified with Co-L@RGO(1:1) (Co-L@RGO(1:1)/GCE) exhibited a low limit of detection (LOD) of 7.24 nM for CGA within the concentration of 0.1-2 µM and 2-20 µM. Co-L@RGO(1:1)/GCE also showed excellent selectivity, stability, and reproducibility for the CGA detection. Co-L@RGO(1:1)/GCE could detect the CGA in honeysuckle with satisfactory results. This work provided a great example for the thiacalix[4]arene-based MOF in the application of electrochemical sensors.

Thiacalix[4]arene-based complex with Co(II) ions as electrode modifier for simultaneous electrochemical determination of Cd(II), Pb(II), and Cu(II).

A complex [Co4(TCTA)2(H2O)8]∙10H2O (Co-TCTA) based on thiacalix[4]arene derivative has been synthesized for the first time using the solvothermal method. The glassy carbon electrode (GCE) modified with Co-TCTA (Co-TCTA/GCE) could simultaneously determine Cd2+, Pb2+, and Cu2+ at around - 0.75 V, - 0.60 V, and - 0.10 V (vs. ref. Ag/AgCl) and had good stability, selectivity, and reproducibility with relative standard deviation (RSD) of 4.4% for Cd2+, 1.4% for Pb2+, and 5.4% for Cu2+. Co-TCTA/GCE showed wide linear range of 0.4-8.0 µM for Cd2+, 0.4-7.0 µM for Pb2+, and 0.6-6.0 µM for Cu2+ when three ions were determined simultaneously. The limits of detection (LODs) of Cd2+, Pb2+, and Cu2+ were 0.071 µM, 0.022 µM, and 0.021 µM, respectively. Moreover, the sensor was used to determine three ions in lake water sample with satisfactory recoveries of 93.6-93.8% for Cd2+, 93.8-103.3% for Pb2+ and 94.6-95.3% for Cu2+. The good adsorption capacity of Co-TCTA and Co(II)/Co(0) circular mechanism on the surface of the electrode were proposed to enhance the electrochemical signals. This work enriched the theoretical research on the complexes for the determination of heavy metal ions.

Single-Component White Light Emission from a Metal-Coordinated Cyclotriveratrylene-Based Coordination Polymer.

A coordination polymer, namely, [Cd3L(H2O)3]·DMA·4H2O (1) (DMA = N,N-dimethylacetamide), was prepared by the solvothermal reaction of cyclotriveratrylene-based ligand 5,6,12,13,19,20-hexacarboxy-methoxy-cyclotriveratrylene (H6L) and Cd(NO3)2·4H2O. In 1, a two-dimensional structure was constructed by the connection of hexanuclear Cd-O clusters and L6- anions. Photoluminescence measurements indicated that 1 displayed tunable photoluminescence through the variation of the excitation wavelength. Significantly, the white light emission of 1 can be observed with a broad excitation wavelength range from 320 to 385 nm. When 1 is excited by 385 nm light, its chromatic coordinate is (0.29, 0.34), which is located very close to the pure white light region (0.33, 0.33). Meanwhile, the color temperature (CCT) is 7994 K, which corresponds well to "cold" white light.

Simultaneous electrochemical detection of gallic acid and uric acid with p-tert-butylcalix[4]arene-based coordination polymer/mesoporous carbon composite.

Design and synthesis of an efficient electrocatalyst for simultaneous determination of gallic acid (GA) and uric acid (UA) is vital in the biological field. Herein, we synthesized a new p-tert-butylcalix[4]arene-based metal-organic electrocatalyst (Mn-L@MC) by combining Mn-L (H4L = tetrakis[(2-biphenylcarboxyl)oxy]-p-tertbutylcalix[4]arene) and mesoporous carbon (MC) via a simple mechanical grinding method. Synergistic effect between Mn-L and MC made the Mn-L@MC composite behave high-efficiency electrocatalytic performance toward simultaneous detection of GA and UA. Under optimal experimental conditions, the Mn-L@MC-2 electrode material featured relatively wide linear range (0.5-90 µM) for the two analytes, and low determination limits of 0.043 µM for GA and 0.059 µM for UA. The remarkable electrochemical detection behavior of Mn-L@MC-2 electrode material toward GA and UA are comparable to those known sensors containing precious metals. The Mn-L@MC-2 material exhibited high selectivity, superior reproducibility, and acceptable stability during the determination of the two analytes. The sensor was assembled to simultaneously detect GA and UA in healthy human urine with satisfactory recoveries.

Two new calix[4]resorcinarene-based coordination cages adjusted by metal ions for the Knoevenagel condensation reaction.

Two new calix[4]resorcinarene-based coordination cages, namely, [Zn4(TPC4R)(PDC)4]·2DMF·6H2O (1-Zn) and [In11(TPC4R)2(PDC)16(µ2-OH)2(H2O)2]·[(CH3)2NH2]·8DMF·20H2O·EtOH (2-In), have been synthesized via solvothermal reactions (TPC4R = tetra(2-(4H-pyrazol-3-yl)pyridine)calix[4]resorcinarene, H2PDC = 3,5-pyridinedicarboxylic acid, DMF = N,N'-dimethylformamide). By carefully tuning different metal ions, two structurally different cages 1-Zn and 2-In were achieved. The former shows a bowl-shaped structure, while the latter features a dumbbell-like structure. After activation, they exhibited unsaturated Zn(ii) or In(iii) Lewis acid sites and the free nitrogen Lewis base sites of the PDC2-. Therefore, they were employed as catalysts for the Knoevenagel condensation reaction in the absence of a solvent. Particularly, 1-Zn featured high structural stability and enhanced the catalytic activity.

A Porous Metal-Organic Framework as an Electrochemical Sensing Platform for Highly Selective Adsorption and Detection of Bisphenols.

The design of artificial receptors with a specific recognition function and enhanced selectivity is highly desirable in the electrochemical sensing field, which can be used for detection of environmental pollutants. In this facet, metal-organic frameworks (MOFs) featured adjustable porosities and specific host-guest recognition properties. Especially, the large hydrophobic cavity formed in the porous MOFs may become a potential artificial receptor. We herein designed a new porous MOF [Zn2(L)(IPA)(H2O)]·2DMF·2MeOH·3H2O (Zn-L-IPA) by using a functionalized sulfonylcalix[4]arene (L1) and isophthalic acid (H2IPA) (DMF = N,N'-dimethylformamide). The specific pore size and pore shape of Zn-L-IPA made it efficiently selective for absorption of bisphenol A (BPA), bisphenol F (BPF), and bisphenol S (BPS). Therefore, a rapid, highly selective, and ultrasensitive electrochemical sensing platform Zn-L-IPA@GP/GCE was fabricated by using Zn-L-IPA as a host to recognize and absorb bisphenol guests (GP = graphite powder, GCE = glassy carbon electrode). Most strikingly, the extremely low detection limits were up to 3.46 and 0.17 nM for BPA and BPF, respectively, using the Zn-L-IPA@GP/GCE electrode. Furthermore, the "recognition and adsorption" mechanism was uncovered by density functional theory with the B3LYP function. This work offered a prospective strategy for selective absorption and detection of harmful bisphenols with the MOF-based porous material.

Self-Assembly of Polyoxometalate-Resorcin[4]arene-Based Inorganic-Organic Complexes: Metal Ion Effects on the Electrochemical Performance of Lithium Ion Batteries.

With their adjustable structures and diverse functions, polyoxometalate (POM)-resorcin[4]arene-based inorganic-organic complexes are a kind of potential multifunctional material. They have potential applications for lithium ion batteries (LIBs). However, the relationship between different coordinated metal ions and electrochemical performance has rarely been investigated. Here, three functionalized POM-resorcin[4]arene-based inorganic-organic materials, [Co2 (TMR4 A)2 (H2 O)10 ][SiW12 O40 ]⋅2 EtOH⋅4.5 H2 O (1), [Ni2 (TMR4 A)2 (H2 O)10 ][SiW12 O40 ]⋅4 EtOH⋅13 H2 O (2), and [Zn2 (TMR4 A)2 (H2 O)10 ][SiW12 O40 ]⋅2 EtOH⋅2 H2 O (3), have been synthesized. Furthermore, to enhance the conductivities of these compounds, 1-3 were doped with reduced graphene oxide (RGO) to give composites 1@RGO-3@RGO, respectively. As anode materials for LIBs, 1@RGO-3@RGO can deliver very high discharge capacities (1445.9, 1285.0 and 1095.3 mAh g-1 , respectively) in the initial run, and show discharge capacities of 898, 665 and 651 mAh g-1 , respectively, at a current density of 0.1 A g-1 over 100 runs. More importantly, the discharge capacities of 319, 283 and 329 mAh g-1 were maintained for 1@RGO-3@RGO even after 400 cycles at large current density (1 A g-1 ).

Three Resorcin[4]arene-Based Two-Dimensional Zn(II) Supramolecular Isomers Synthesized via a Structure-Directing Strategy for Knoevenagel Condensation.

Herein, in the presence of three structure-directing agents (SDAs), a family of imidazole-functionalized resorcin[4]arene-based coordination polymers (CPs), [Zn(TIC4R)(HCOO)]·HCOO·0.5DMF·1.5H2O (1), [Zn(TIC4R)(CN)]·HCOO·DMF·2.5H2O (2), and [Zn(TIC4R)(H2O)]·2HCOO·2H2O (3), were assembled under solvothermal conditions [TIC4R = tetra(imidazole) resorcin[4]arene]. 1 exhibits a double-layer structure with rectangle windows, and 2 and 3 display monolayer structures. The layers of CPs 2 and 3 are slides with different offsets along the a-axis. In addition, three CPs were used as catalysts to catalyze Knoevenagel condensations. Strikingly, all CPs exhibit remarkable catalytic performance for several substrates. To the best of our knowledge, this is the first time that a small organic acid as SDA was used in the syntheses of resorcin[4]arene-based supramolecular isomers.

A calix[4]resorcinarene-based giant coordination cage: controlled assembly and iodine uptake.

Construction of large multi-component coordination cages becomes much more challenging as the number of building blocks increases. A giant hexameric calix[4]resorcinarene-based coordination cage (cage-1) was successfully designed through the precise tuning of ancillary rigid tetracarboxylic acid. Significantly, cage-1 exhibited reversible uptake of volatile iodine, suggesting that it could serve as a porous material for efficient capture and separation of radioactive iodine.

Highly Stable Copper(I)-Based Metal-Organic Framework Assembled with Resorcin[4]arene and Polyoxometalate for Efficient Heterogeneous Catalysis of Azide-Alkyne "Click" Reaction.

A new highly stable copper(I)-based metal-organic framework (MOF), namely, [CuI4(SiW12O40)(L)]·6H2O·2DMF (1), was synthesized by incorporating Keggin-type polyoxometalate (POM) anions and a functionalized wheel-like resorcin[4]arene-based ligand (L) under sovothermal condition. 1 exhibits a charming 3D supramolecular architecture sandwiched by the POM anions. Noticeably, 1 has exceptional chemical stability, especially in organic solvents or aqueous solutions with a wide range of pH values. Considering the catalytically active Cu(I) sites in 1, the azide-alkyne cycloaddition (AAC) reaction was studied by employing 1 as the heterogeneous catalyst. Most strikingly, 1 exhibits excellent catalytic activity as well as recyclability for the AAC reaction.

Versatile Assembly of Metal-Coordinated Calix[4]resorcinarene Cavitands and Cages through Ancillary Linker Tuning.

We propose a design strategy for assembly of metal-coordinated calix[4]resorcinarene cavitands and cages by tuning of the ancillary linkers. Assembly of newly functionalized cavitand with angular isophthalic acid analogs affords three intriguing metal-coordinated cavitands with deep cavities, 1a-1c. Further, by mediating appropriate spacers between two isophthalic acids, two bowl-shaped cavitands are successfully joined together to produce three elegant coordination cages with tunable sizes and shapes, 2a-2c. The cavitand and cage crystals possess considerable amount of accessible porosities, as clearly established by gas adsorption measurements. Remarkably, 1a-1c also exhibit high structural flexibilities, reversibly transforming between the open-pore and the narrow-pore structures, upon removal and sorption of guest molecules, as evidenced by diffraction and gas adsorption measurements. By combining experimental studies with density functional theory (DFT) calculations, we thoroughly elucidated the mechanism of the structural transformations in response to external stimuli in this new class of flexible porous solids.