Journal of Water Process Engineering
·
2023
·
IF 7
Caifeng Wei,Yanqin Cai,Zujin Yang
The presence of heavy metal ions and organic dyes in aqueous solutions has a significant impact on the ecological environment and human health. Herein, a novel bifunctional imidazolium-based porous organic polymer (IMSPF-Br-C=C) was prepared successfully via quaternization reaction of spirobifluorene and 1,4-dibromo-2-butene. The synthesized material was characterized by scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), Fourier transform infra-red spectra (FTIR), Thermogravimetric analysis (TGA), X-ray diffraction (XRD), N 2 adsorption-desorption analysis and solid-state 13 C CP/MAS NMR spectroscopy, confirming its structure and stability. Owing to the conjugated structure of spirobifluorene, IMSPF-Br-C=C showed excellent recognition performance for dichromate anion (Cr 2 O 7 2− ) with the limit of detection (LOD) of 1.58 μmol/L. In addition, IMSPF-Br-C=C with the abundant imidazolium cations showed the outstanding adsorption performance in the removal of Cr 2 O 7 2− and methyl orange (MO). Removal efficiencies and adsorption capacities of IMSPF-Br-C=C were 98.3 % and 99.4 %, 452.8 and 1304.2 mg/g in 6 min, respectively. The results show that the electrostatic interactions and π-π stacking play crucial roles in the fluorescence detection of Cr 2 O 7 2− and adsorptive separation of Cr 2 O 7 2− and MO. Furthermore, physico-chemical techniques, density functional theory (DFT) calculation and frontier molecular orbital theory (FMO) were used to explain action mechanism. This work provides a cost-effective IMSPF-Br-C=C as a bifunctional platform for sensing Cr 2 O 7 2− and adsorptive separation of Cr 2 O 7 2− and MO in aqueous solution.
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JOURNAL OF MOLECULAR STRUCTURE
·
2025
·
IF 4.7
Chun Liu,Xin-Long Ni
A unique phenypyridine derivatives fluorescent probes ( G1, G2, G3 and G4) were constructed and the detection performance of Cr 2 O 7 2- anion was studied. In aqueous solution, we found that the fluorescence emission of anthracene phenypyridine derivatives can be quenched by the non-covalent interaction (NCI) of anthracene phenypyridine with Cr 2 O 7 2- , and other common anions and cations do not interfere with the quenching process. Theoretical calculation shows that the LUMO energy level of Cr 2 O 7 2- is similar to that of anthracene phenylpyridium molecules, so that after G1 and Cr 2 O 7 2- molecules combine to form an ion pair (Cr 2 O 7 2- @ G1 ), the LUMO orbital of G1 is delocalized toward Cr 2 O 7 2- , which makes the HOMO electron of the probe easily captured by Cr 2 O 7 2- when it is photo excited. Intermolecular charge transfer (CT) occurs, which is resulting in fluorescence quenching of dye molecules. The discovery of this phenomenon provides a reference for the design of water-soluble anionic fluorescent probes.
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MOLECULES
·
2022
·Vol. 27
·期 13
·4294
·
IF 4.927
Hui Li,Fei Li,Fang Liu,Xiao Chen,Wenyuan Xu,Liang Shen,Jingkun Xu,Rui Yang,Ge Zhang
In view of that conjugated polymers (CPs) are an attractive option for constructing high-sensitive Cr2O72−sensors but suffer from lacking a general design strategy, we first proposed a rational structure design of CPs to tailor their sensing properties while validating the structure-to-performance correlation. Short side chains decorated with N and O atoms as recognition groups were instructed into fluorene to obtain monomers Fmoc-Ala-OH and Fmoc-Thr-OH. Additionally, their polymersP(Fmoc-Ala-OH)andP(Fmoc-Thr-OH)were obtained through electrochemical polymerization.P(Fmoc-Ala-OH)andP(Fmoc-Thr-OH)with high polymerization degrees have an excellent selectivity towards Cr2O72−in comparison to other cations and anions. Additionally, their limit of detection could achieve 1.98 fM and 3.72 fM, respectively. Especially, they could realize the trace detection of Cr2O72−in agricultural products (red bean, black bean, and millet). All these results indicate that short side chains decorated with N and O atoms functionalizing polyfluorene enables the ultra-trace detection of Cr2O72−. Additionally, the design strategy will spark new ideas for the construction of highly selective and sensitive Cr2O72−sensors.Keywords:Cr2O72−;design strategy;conjugated polymer;ultra-trace detection;agricultural products
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NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 48
·22915-22923
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IF 3.591
Jing Li,Lin-Hui Wu,Shu-Li Yao,Hui Xu,Teng-Fei Zheng,Sui-Jun Liu,Jing-Lin Chen,He-Rui Wen
A novel Zn2+-based metal–organic framework (MOF) with the formula {[Zn(μ2-η1:η1-BBIP)(μ2-η1:η1:η1-OBA)]·3H2O}n, denoted as JXUST-7, has been successfully assembled using semi-rigid N-donor 3,5-bis(benzimidazol-1-yl)pyridine (BBIP) and flexible 4,4′-oxybisbenzoate (H2OBA). The adjacent Zn2+ ions are linked through an OBA2− ligand with a μ2-η1:η1:η1 bridging mode to form an infinite one-dimensional (1D) Zn2+–OBA2− chain. The neighbouring 1D chains are further connected by a BBIP ligand with a μ2-η1:η1 bridging mode to gain a two-dimensional (2D) sheet layer structure. Topological analysis indicates that the whole 2D structure of JXUST-7 could be simplified as a uninodal sql topology with a point symbol of {44·62}. Furthermore, the opposite parallel 2D layers are further packed by a face-to-face π–π interaction to generate a three-dimensional supramolecular structure. Luminescence experiments reveal that JXUST-7 could be considered as a multi-responsive MOF-based fluorescent probe toward Fe3+, Cr2O72− and acetylacetone (acac) via the fluorescence quenching (turn-off) effect. The detection limits for Fe3+, Cr2O72− and acac are 0.14, 1.33 and 6.53 ppm, respectively. The fluorescence quenching mechanism was analyzed in detail by powder X-ray diffraction, fluorescence lifetime measurement, X-ray photoelectron spectra, theoretical calculation and UV-Vis absorption spectra. More importantly, JXUST-7 could be cyclically utilized at least five times for detecting Fe3+, Cr2O72− and acac.
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Analytical Methods
·
2020
·Vol. 13
·期 3
·390-398
·
IF 2.596
Qiaoqiao Wen,Congjie Pan,Xuezhen Qin,Qiujuan Ma,Suxiang Feng
Chromium (Cr(VI)), a highly toxic metal-oxyanion which is carcinogenic and mutagenic to humans, is a severe environmental pollutant. Developing simple methods for sensitive and selective detection of Cr(VI) is of great significance. In this work, fluorescent silicon nanoparticles (SiNPs) with good water solubility were facilely synthesized via a one-step hydrothermal method by using (3-aminopropyl)triethoxysilane (APTES) as the silicon source and natural antioxidant quercetin as the reducing agent. The obtained SiNPs displayed good thermostability, salt-tolerance and photo-stability. The as-prepared SiNPs exhibited bright blue emission at 437 nm under excitation at 362 nm, allowing them to be developed as a fluorescent probe for detection of Cr2O72−. Significantly, the fluorescence of the SiNPs could be remarkably quenched by Cr2O72−via the internal filtering effect (IFE). Based on this phenomenon, a novel fluorescence method for detection of Cr2O72− was established. A good linear relationship was obtained from 0.5 to 100 μM with a limit of detection (based on 3 s/k, LOD) of 180 nM. The proposed fluorescence method was successfully applied to the detection of Cr2O72− in tap water. Moreover, a fluorescent filter paper sensor was developed for the visual detection of Cr2O72−, providing a valuable platform for Cr2O72− sensing in a convenient way.
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INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Linfeng Liang,Jianan Cui,Xinrong Han,Yinkang Ding,Jing Yang,Sanhu Zhao,Huan Li
Previously, we reported a 1,3,5-triazine-based metal–organic framework (MOF) constructed via the in situ hydrolysis of melamine. However, the use of template molecules within the pores posed significant challenges for material activation and resulted in pronounced fluorescence quenching. In this work, we introduce a more sustainable and template-free synthetic strategy by directly employing ammeline as the organic ligand to construct a triazine-based MOF, SXU-120(ammeline). This approach simplifies the activation process, enhances solid-state fluorescence, and improves stability. The resulting MOF demonstrates high sensitivity and selectivity for aqueous Cr2O72– ions, achieving a Stern–Volmer quenching constant (KSV) of 5.13 × 104 M–1. Furthermore, a scalable reflux-based synthesis route was developed, reinforcing the material’s potential for practical and eco-friendly environmental sensing applications.
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DYES AND PIGMENTS
·
2021
·
IF 4.889
Fei Li,Xuemin Duan,Shuxin Hu,Long Zhang,Liang Shen,Fang Liu,Hui Li,Ge Zhang,Jingkun Xu
Hexavalent chromium (Cr(VI)) pollution is related to human health, and the detection of its concentration has a decisive effect on pollution treatment. In this work, we designed a Cr 2 O 7 2− sensor P(Fmoc-Osu) and applied it in farmland. In the boron trifluoride diethyl etherate solution, the monomer Fmoc-Osu was electropolymerized and obtained its conjugated polymer P(Fmoc-Osu) . The introduction of succinimide and carbonic ester group in side chain enabled it to show high selectivity to Cr 2 O 7 2− in comparison to anions and twenty amino acids. Furthermore, by taking advantage of the signal amplification effect of a conjugated polymer, P(Fmoc-Osu) could analyze Cr 2 O 7 2− in trace amounts and the limit of detection was 8.3 fM. For agricultural application, we employed it in farmland water, soil, Chinese cabbage, carrot and the results showed a satisfactory result. All these results showed that P(Fmoc-Osu) is an efficient tool to detect Cr 2 O 7 2− in practical application.
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SOLID STATE SCIENCES
·
2023
·
IF 3.5
Xiaoqin Feng,Huijun Li,Weina Wu,Yuan Wang,Zhouqing Xu,Jia Fu
Herein, a multifunctional mechanochromic Metal-Organic Framework ( HPU-27 ) was designed for detecting water in THF and adsorbing Cr(VI) from contaminated water. The probe displays a reasonable quenching response for H 2 O over a concentration range of 0–80% with a detection limit of 0.039%, accompanied by an obvious fluorescent color transformation from yellow to colorless. The detection mechanism of HPU-27 toward H 2 O was proved as the alternation of the physical states between aggregation and dispersion in THF and H 2 O. Meanwhile, the HPU-27 material showed a good ability to adsorb Cr(VI) from contaminated water. The maximum adsorption capacity is 294.94 mg/g. In addition, the adsorption mechanism was discussed in detail. Thus, we believe that our strategy is promising extensively for the development of multifunctional MOF materials.
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JOURNAL OF SOLID STATE CHEMISTRY
·
2026
·
IF 3.2
Zhi Shen,Hai-bin Zhang,Pei-Xuan Zhang,Xin-Yue Zhang,Shan-shan Liu,Feng-pu Cao,Qiang Zhao
In order to enrich the rare earth functional materials with fluorescence and magnetic properties, [(M·cpipa·2H 2 O) ·3.75H 2 O] n (M = Pr( 1 ), Eu( 2 ), Gd( 3 ), Dy( 4 ), Tm( 5 ) and Y( 6 )) six three-dimensional porous coordination polymers with the same structure were synthesized by solvothermal method using tridentate carboxylic acid ligand (5-(2-carboxyphenoxy)isophthalic acid (H 3 cpipa)) as the building blocks and combining with rare earth metal salts of Pr, Eu, Gd, Dy, Tm and Y in this paper. The structures of the complexes were characterized by elemental analysis and powder X-ray diffraction, and their solid-state fluorescence and magnetic properties were systematically tested. The results show that the complex 2 exhibits significantly enhanced fluorescence characteristics compared to the ligand, emitting bright red fluorescence under ultraviolet light excitation; its aqueous dispersion has excellent recognition selectivity for Cr 2 O 7 2− , K sv values of complex 2 is 7.7 × 10 3 M −1 and the detection limit is 0.055 μM. Magnetic tests show that complexes 1 , 4 , 5 exhibit antiferromagnetic interactions and complex 3 exhibits ferromagnetic behavior. This study provides new candidate materials and experimental basis for the application of rare earth complexes in fluorescence sensing and molecular magnetism.
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Nanoscale
·
2017
·Vol. 9
·期 48
·19139-19144
·
IF 7.367
Jianjun Du,Haoying Ge,Quanyong Gu,Hong Du,Jiangli Fan,Xiaojun Peng
In this work, an N-T/gold nanoparticle system was assembled for the convenient and colorimetric identification of Cr based on its coordination chemistry with the thymine derivative (N-T). In addition to the visible colorimetric changes for the qualitative Cr identification, the A630 nm/520 nm values changed linearly with Cr concentration over a range of 0.5–2.5 μM and the detection limits reached 0.03 μM and 0.07 μM for Cr3+ and Cr2O72−, respectively, both of which satisfied the Cr water quality standards of the U.S. EPA, WHO and China. Furthermore, a more convenient method was developed for quantitative determination of Cr concentrations in practical samples based on the Eyedropper function in Microsoft's PowerPoint software, wherein the RGB (red, green and blue) value of the sample could be easily screened in the colorimetric card for a more accurate result with good recovery, avoiding complicated instrumentation.
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ACS Applied Nano Materials
·
2022
·
IF 6.14
Shu-Na Liu,Han-Ni Wang,Min-Liang Feng,Kai-Ling Yang,Songliang Cai,Jun Fan,Wei-Guang Zhang,Sheng-Run Zheng
The covalent linking of metal–organic cages (MOCs) with a nanoscale cavity is an efficient strategy to construct functional materials with different properties compared with bulk MOCs, but studies based on this topic are still less explored. In addition, toxic chemical and pollutant uptake, especially iodine vapor adsorption on MOC-based materials, still lacks investigation. Herein, an MOC-extended amorphous network (denoted MOC–DASD) via the covalent linking of an aldehyde-functionalized cationic Pd12L24 MOC (with about 3.5 nm in diameter) with an anionic organic linker, 4,4′-diamino-2,2′-stilbenedisulfonic acid (DASD), was constructed and applied to absorb Cr2O72– in water and capture I2 molecules in vapor. The covalent linkage of MOC and DASD via C═N bonds was confirmed by IR, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and ζ-potential tests. In addition, the original NO3– anions can be easily removed from the MOC–DASD due to the introduction of an anionic linker, thus releasing more effective cavities for guest adsorption. Although there is a lack of exchangeable anions, MOC–DASD still exhibits the ability to capture Cr2O72– in water with moderate capacity and high selectivity. In addition, the MOC–DASD showed a significantly enhanced iodine vapor uptake capacity. The iodine uptake capacity of MOC–DASD reached 3.67 g/g, which is 1.8 times higher than that of bulk MOC. A mechanistic study shows that some of the iodine was closely adsorbed by charge transfer. The release of iodine at 120 °C reveals that approximately 74% of the absorbed iodine can be removed, and the MOC can uptake the iodine again with a capacity of 1.5 g/g, showing good reusability.
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ANALYTICA CHIMICA ACTA
·
2021
·
IF 6.558
Kuan-Neng Chi,Yan Guan,Xi Zhang,Tong Yang,Shuang Meng,Rong Hu,Yun-Hui Yang
The analytical methods based on colorimetric detection of various analytes have attracted intensive interest. However, most of them display relatively low sensitivity. Herein, a novel colorimetric strategy based on iodide/metal-organic frameworks (MOF)-mediated amplification was developed for low-cost, naked-eye detection and quantification of H 2 O 2 ,Cr 2 O 7 2− , and H 2 S. Cu-MOFs could catalyze the oxidation of the colorless peroxidase substrate TMB to produce a blue product. The published researches mainly focused on the immobilization or integration of a macromolecule , such as natural enzymes , to enhance MOFs catalytic abilities. The use of small molecules to improve the catalytic performance of MOFs has rarely reported. Due to the negligible steric hindrance , iodide could easily be adsorbed in the framework pore of MOFs to conduct the synergic catalytic effect, and shows a high catalytic effect. As a result, the catalytic activity of Cu-MOFs was dramatically enhanced, and thus, the nanocatalyst could act as an amplifier system for target detection. The detection limits obtained by the amplified method are 25, 30, and 0.2 nM, respectively, which are about 200-fold lower than that of the unamplified colorimetric assays . The colorimetric strategy developed herein provides a novel system for the detection of low concentrations of analytes in complex biological samples.
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