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ANALYTICA CHIMICA ACTA · 2017 · IF 4.95

Design of a calix[4]arene-functionalized metal-organic framework probe for highly sensitive and selective monitor of hippuric acid for indexing toluene exposure

Yaran Du,Xiqian Li,Haijiao Zheng,Xueju Lv,Qiong Jia

In the present work, a novel metal-organic framework (MOF) fluorescent probe was prepared by post-synthetic modification of MIL-53-NH 2 (Al) with carboxylatocalix[4]arene (CC[4]A). The introduced CC[4]A could not only enhance the fluorescence performance and the recognition ability of the probe, but also sustain the high stability under UV light and moisture conditions. A method based on the as-synthesized CC[4]A@MIL-53-NH 2 (Al) probe was established for sensing hippuric acid . The detection limit was determined to be as low as 3.7 μg mL −1 . Over the concentration range of 0.005–3 mg mL −1 , the calibration curve was obtained with a satisfactory linearity ( R 2  = 0.993). The method was successfully used for rapid and highly selective direct monitor of hippuric acid in human urine. The sensor had great potential to be used as a simple diagnostic tool for hippuric acid in human urine which is regarded as a biological index of toluene exposure.

研究领域: 化学 · 材料科学 · 分析化学 · 环境科学
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MOLECULES · 2017 ·Vol. 22 ·期 5 ·783 · IF 2.861

Inclusion Complexes of a New Family of Non-Ionic Amphiphilic Dendrocalix[4]arene and Poorly Water-Soluble Drugs Naproxen and Ibuprofen

Khalid Khan,Syed Lal Badshah,Nasir Ahmad,Haroon Ur Rashid,Yahia Mabkhot

The inclusion complexes of a new family of nonionic amphiphilic calix[4]arenes with the anti-inflammatory hydrophobic drugs naproxen (NAP) and ibuprofen (IBP) were investigated. The effects of the alkyl chain’s length and the inner core of calix[4]arenes on the interaction of the two drugs with the calix[4]arenes were explored. The inclusion complexes of Amphiphiles1a–cwith NAP and IBP increased the solubility of these drugs in aqueous media. The interaction of1a–cwith the drugs in aqueous media was investigated through fluorescence, molecular modeling, and1H-NMR analysis. TEM studies further supported the formation of inclusion complexes. The length of lipophilic alkyl chains and the intrinsic cyclic nature of cailx[4]arene derivatives1a–cwere found to have a significant impact on the solubility of NAP and IBP in pure water.Keywords:amphiphilic calix[4]arene;naproxen;ibuprofen;solubility;inclusion complexes

研究领域: 药物化学 · 药剂学
✓ 已验证 DOI PubMed 高影响因子
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2011 · IF 1.77

A novel spectrofluorometric method for the determination of methiocarb using an amphiphilic p-sulfonatocalix[4]arene

Xue-Ping Ding,Dong-Bao Tang,Tao Li,Su-Fan Wang,Yun-You Zhou

The characteristics of host–guest complexation between tetrabutyl ether derivatives of p -sulfonatocalix[4]arene (SC4Bu) and methiocarb [3,5-dimethyl-4-(methylthio) phenyl methylcarbamate] were investigated by fluorescence spectrometry. Upon addition of methiocarb, the fluorescence intensity of SC4Bu was quenched regularly and a slight red shift was observed for the maximum emission peak. These results indicated that the SC4Bu-methiocarb complex was formed a 1:1 mole ratio. An association constant of 1.67   ×   10 4   L   mol −1 was calculated by applying a deduced equation. The interaction mechanism of the inclusion complex was discussed. Based on the results, a novel spectrofluorimetric method was described for the determination of methiocarb with a detection limit at 0.05   μg   mL −1 . This method is very simple and shows high sensitivity and selectivity. Moreover, the proposed method was successfully applied to the determination of methiocarb in water samples.

CAS / MDL: 2032-65-7
研究领域: 分析化学 · 环境科学
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Journal of Water Process Engineering · 2022 · IF 7.34

Phosphorylated hyper-crosslinked calix[4]arene for selective uranyl extraction from seawater

Xiying Zhu,Lijia Liu,Yudan Wang,Fuqiu Ma,Yao Tian,Hongxing Dong,Chunhong Zhang

Seawater contains abundant uranium, which could provide a long–term supply for developing the nuclear power industry. Developing an efficient uranium–selective adsorbent is therefore an urgent requirement. In this work, we used a simple Friedel–Crafts alkylation reaction and a subsequent phosphorylation reaction to prepare porous phosphorylated hyper-crosslinked calix[4]arene (C4HP) for potential use in the recovery of uranium from seawater. The effect of the initial pH, adsorbent composition, sorbent dose and contact time on the sorption of uranyl ions was investigated. Because of the introduction of the phosphate groups , C4HP shows an excellent adsorption capacity of 336.4 mg·g −1 for uranium, which is much higher than that of hyper-crosslinked calix[4]arene (C4H) without phosphorylation. Meanwhile, C4HP functioned as a promising adsorbent for uranyl extraction with fast capture kinetics (the adsorption equilibrium can be reached in 150 min). After 6 cycles, C4HP maintained its original adsorption capacity of 76.2 % (255.4 mg·g −1 ). Furthermore, C4HP possesses excellent adsorption selectivity for uranium in artificial seawater, with a K d U of ~4.1 × 10 4  mL·g −1 , much higher than that of other metals. This makes it useful for broad applications and capturing uranium from natural seawater. The effective extraction of uranyl was primarily attributed to the chelation of uranyl ions with phosphate groups .

研究领域: 材料科学 · 环境科学 · 核能技术
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2024 ·Vol. 333 ·期 3 ·1263-1274 · IF 1.5

Sensitive fluorescent determination of uranyl ions using a terbium (III) 4-sulfocalix[4]arene probe

Zhou Xiayu,Gong Mi,Xiong Lihao,Wang Yue,Jiang Wenting,Song Jiayi,Liu Jinquan,Dai Zhongran,Yang Shengyuan,Zhen Deshuai,Li Le

Uranium, regarded as an important element in nuclear fission energy schemes, is harmful to public health owing to its high toxicity and radioactivity. Herein, a novel fluorescent probe (SC4A@Tb 3+ ) was developed using a one-step liquid-phase method with 4-sulfocalix[4]arene (SC4A) and rare earth–metal ions (Tb 3+ ) as precursors to realize the accurate monitoring of uranyl ion (UO 2 2+ ) detection. Based on the dynamic quenching mechanism, the SC4A@Tb 3+ fluorescence quenching sensor for UO 2 2+ detection was in the linear range of 0–0.36 µM, with a detection limit of 20 µg·L −1 , and successfully quantified UO 2 2+ in water and human serum samples. These results suggest that SC4A@Tb 3+ is a potential sensing material for UO 2 2+ detection.

研究领域: 分析化学 · 环境科学 · 放射化学
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PEST MANAGEMENT SCIENCE · 2023 ·Vol. 79 ·期 9 ·3133-3140 · IF 4.1

A general supramolecular adjuvant for pesticides based on host–guest recognition

Rong Ma,Yue-Dan Zheng,Han-Wen Tian,Meng-Meng Chen,Yu-Xin Yue,Qiang Bian,Hua-Bin Li,Dong-Sheng Guo

BACKGROUND Pesticides are indispensable in agriculture and can effectively improve the yields and quality of crops. Due to their weak water solubility, most pesticides need to be dissolved by adding solubilizing adjuvants. In this work, based on molecular recognition of the macrocyclic host, we developed a novel supramolecular adjuvant, called sulfonated azocalix[4]arene (SAC4A), which significantly improves the water solubility of pesticides. RESULTS SAC4A presents multiple advantages, including high water solubility, strong binding affinity, universality, and simple preparation. SAC4A showed an average binding constant value of 1.66 × 10 5 M −1 for 25 pesticides. Phase solubility results indicated that SAC4A increased the water solubility of pesticides by 80–1310 times. The herbicidal, fungicidal, and insecticidal activities of supramolecular formulations were found to be superior to those of technical pesticides, and the herbicidal effects were even better than those of commercial formulations. CONCLUSION Overall results revealed the potential of SAC4A to improve the solubility and effectiveness of pesticides, providing a new development idea for the application of adjuvants in agriculture. © 2023 Society of Chemical Industry.

CAS / MDL: 81-88-9 121-57-3
研究领域: 农业科学 · 化学科学
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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Utilizing 4-Sulfonylcalix[4]arene as a Selective Mobile Phase Additive for the Capture of Methylated Peptides

Jie Shi,Yuting Xiong,Junyan Li,Baolei Gao,Guangyan Qing,Qianying Sheng,Minbo Lan

Protein methylation has attracted increasing attention due to its significant regulatory roles in various biological processes. However, the diversity of methylation forms, subtle differences between methylated and nonmodified sites, and their ultralow abundances pose substantial challenges for capturing and isolating methylated peptides from biological samples. Herein, we develop a chromatographic method that utilizes 4-sulfonylcalix[4]arene (SC4A) as a mobile phase additive and Click-Maltose as the stationary phase to separate methylated/nonmethylated peptides through the adsorption of the SC4A-K(Me3) complex. By utilization of the interaction between calix[4]arene cavities and trimethylated lysine residues, methylated peptides could be specifically separated from peptide samples. This method significantly improves the signal-to-noise ratio (S/N), even in samples containing a 10-fold excess of bovine serum albumin (BSA) trypsin digests. Additionally, we successfully enriched 12 methylated peptides from histone digests. This study paves the way for the selective enrichment of lysine methylated peptides in post-translational modification proteomics (PTMs), enhancing both the capture efficiency and selectivity of methylated peptides and providing robust technical support for subsequent proteomics research.

研究领域: 蛋白质组学 · 生物化学 · 分析化学
✓ 已验证 DOI PubMed 高影响因子
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Journal of Water Process Engineering · 2023 · IF 7

Synthesis of hypercrosslinked calix[4]arenes anchored with Fe(III) via phosphate groups for excellent uranyl extraction from wastewater and seawater

Xiying Zhu,Lijia Liu,Yudan Wang,Fuqiu Ma,Yao Tian,Hongxing Dong,Chunhong Zhang

An ideal adsorption material of uranium with not only a high adsorption capacity and high selectivity but also a broad applicability is required. In this study, a porous Fe(III) complex of phosphorylated hypercrosslinked calix[4]arenes (C4HP-Fe(III)) was synthesized. Anchoring Fe(III) via phosphate groups on phosphorylated, hypercrosslinked calix[4]arene (C4HP) significantly improved the uranium-adsorption performance, as evidenced by a 47.9 % increase in the uranium uptake (the adsorption capacity increased up to 497.6 mg·g −1 in a 60-mg·L −1  U solution). C4HP-Fe(III) is a promising adsorbent for uranyl extraction and exhibits fast capture kinetics (the adsorption capacity sharply increased in the first 30 min, which accounted for 86 % of the total amount of uranyl ions adsorbed). A study on the effect of pH on the uranium adsorption of C4HP-Fe(III) suggested that the adsorption capacity was higher than 300 mg·g −1 in the pH range of 5–10, even in a strongly acidic environment of pH 3–4, and it also had a specific adsorption capacity (≥ 168.2 mg·g −1 ). Furthermore, C4HP-Fe(III) possesses excellent ion selectivity for uranyl in simulated wastewater and simulated seawater, and the K d U can reach 4.1 × 10 3  mL·g −1 and 4.4 × 10 4  mL·g −1 , respectively. After 6 cycles, C4HP-Fe(III) maintained its original adsorption capacity of 92.2 %. This makes it useful for wide applications and can be used for capturing uranyl ions from industrial wastewater and natural seawater. The effective extraction of uranyl was mainly attributed to the chelation of uranyl ions with both phosphate groups and active hydroxyl groups (due to the introduction of Fe 3+ ).

CAS / MDL: 10025-77-1
研究领域: 环境科学 · 材料科学
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Soft Matter · 2023 ·Vol. 19 ·期 30 ·5711-5722 · IF 3.4

Improvement effect of p-sulfonatocalix[4]arene on the performance of the PEG/salt aqueous two-phase system

Yanrong Cheng,Wenlin Xu,Yaqiong Wang,Xia Guo

The PEG/salt aqueous two-phase system (ATPS) is the most common ATPS, but its application is still limited due to the restricted polarity difference between the two phases and the poor enhancement effect of adjuvants on ATPS performance so far. Unlike the adjuvants used so far, calixarenes can bind ions and molecules via multiple noncovalent interactions. In the present study, a water-soluble calixarene, p-sulfonatocalix[4]arene (SC[4]), was used for the first time as the adjuvant to improve the performance of the PEG 600/(NH4)2SO4 ATPS through multiple interactions. It is found that when the SC[4] and the SC[4]/imidazole ionic liquid ([Cnmim]Br) complex were used as the adjuvants, the formation of PEG 600/(NH4)2SO4 ATPS was enhanced, and the transfer of the extracts (including S-mandelic acid, L-tryptophan, and L-phenylalanine) into the PEG phase was promoted. Moreover, although the single [Cnmim]Br, a commonly used adjuvant, does not promote the migration of the target molecules into the polymer phase, the SC[4]/[Cnmim]Br complex is superior to SC[4] in enhancing the performance of the ATPS because the SC[4]/[Cnmim]Br aggregates enable more binding sites to combine with the extract. Besides, the partition coefficient of SC[4] in the PEG/trisodium citrate ATPS is much smaller than that in the PEG/(NH4)2SO4 ATPS, which is helpful for the recovery of extracts into the citrate phase.

CAS / MDL: 25322-68-3 63-91-2
研究领域: 生物化学 · 分离科学
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FOOD CHEMISTRY · 2024 · IF 8.5

Host-guest mediated recognition and rapid extraction of Fusarium mycotoxins in cereals by nickel ferrite magnetic calix[4]arene-derived covalent organic framework fabricated in room-temperature

Jiana Lin,Gongke Li,Yuling Hu,Qisheng Zhong

Fusarium mycotoxins are toxic secondary fungal metabolites and widely distributed in cereals. Herein, a nickel ferrite magnetic calix[4]arene-derived covalent organic framework (NiFe 2 O 4 @CX4-COF) was meticulously designed and synthesized using a room-temperature method for the enrichment of mycotoxins. The CX4-COF exhibited a porous crystalline network with an eclipsed AA-stacking configuration. The ingenious integration of NiFe 2 O 4 , supramolecular calix[4]arene and COF contributed to host-guest mediated recognition, size-selectivity and high adsorption capacity, rapidly reaching adsorption equilibrium within only 3 min. Simulation calculations revealed that the host-guest interaction, size effect and abundant binding sites facilitated synergistically recognize and capture mycotoxins. NiFe 2 O 4 @CX4-COF has successfully applied for simultaneous extraction and analysis of mycotoxins in cereals, achieving negligible matrix effects (−14% to 13%), high sensitivity (LODs of 0.003–0.014 μg/L) and satisfactory recoveries (74.4%–116%). This work provides a prospective platform for constructing tailored macrocycle-based COFs under mild conditions for precise recognition and accurate analysis of trace hazardous substances in food.

研究领域: 食品科学 · 分析化学 · 材料科学
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MICROCHIMICA ACTA · 2025 ·Vol. 192 ·期 3 ·1-14 · IF 5.3

Smartphone-assisted fluorescence/colorimetric dual-mode sensing strategy for uranium ion detection using cerium-sulfonyl calix[4]arene

Xiong Lihao,Tong Yuqi,Song Jiayi,Chen Sihan,Liu Yu,Liu Jinquan,Li Le,Zhen Deshuai

A novel fluorescence/colorimetric dual-mode detection strategy for uranium ions (UO 2 2+ ) is presented based on a cerium-sulfonyl calix[4]arene (SC4A) platform. The exo- and endo-rim sites of SC4A can coordinate with Ce 3+ and Ce 4+ ions, respectively, quenching Ce 3+ fluorescence and influencing the oxidase-like activity of Ce 4+ . In the absence of UO 2 2+ , the solution of 3,3,5,5-tetramethylbenzidine (TMB) remains blue, but upon UO 2 2+ binding, Ce 3+ dissociates from SC4A, restoring fluorescence, while UO 2 2+ interacts with oxTMB, turning the solution from blue to colorless. This dual-mode system provides a linear fluorescence detection range of 30–800 nM with a detection limit of 20.20 nM, and a colorimetric range of 30–800 nM with a detection limit of 27.78 nM. By combining high-sensitivity fluorescence with visual colorimetric analysis, the proposed method possesses high sensitivity, accuracy, and reliability. Notably, smartphone-based color capture facilitates rapid and convenient sample analysis, enabling straightforward quantification at varying UO 2 2+ concentrations. The method has been successfully applied to real water and urine samples, demonstrating its practical utility in environmental and biological monitoring of UO 2 2+ . Graphical abstract

研究领域: 分析化学 · 环境科学 · 生物医学工程
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Inorganic Chemistry Frontiers · 2021 ·Vol. 8 ·期 22 ·4903-4913 · IF 6.569

Hexylresorcinol calix[4]arene-assisted synthesis of ZnO–Au micro–nano materials with enhanced photodegradation performance to degrade harmful organic compounds

Yufeng Yao,Jiayi Yuan,Ming Shen,Bin Du

In this study, hexylresorcinol calix[4]arene-ZnO-Au (HRCA-ZnO-Au) micro–nano materials are synthesized by a simple atmospheric reflux. AuCl4− ions are in situ reduced to Au by the phenolic hydroxyl groups of amphiphilic HRCA and deposited on the primarily formed ZnO sheets, which prevents Zn2+ ions in the solution from depositing at this position. Finally, the flake sample is obtained. HRCA and chloroauric acid effectively shape the morphology of ZnO from micron-sized flowers to nanometer sheets, and they significantly increase the specific surface area of the sample. Low temperature calcination of the HRCA-ZnO-Au composite micro–nano materials partially removes calixarene molecules and exposes the surface of ZnO–Au. Thus, the photocatalytic activity of ZnO–Au is significantly improved due to the synergistic effect between ZnO and Au.

研究领域: 材料科学 · 环境科学
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