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Progress in Chemistry 2019, Vol. 31 Issue (1): 191-200 DOI: 10.7536/PC180527 Previous Articles   Next Articles

• Review •

Application of Food and Water Samples Pretreatment Using Functional Metal-Organic Frameworks Materials

Lei Bai1,2, Yanfeng Wang1,2, Shuhui Huo1,2,**(), Xiaoquan Lu1,2,**()   

  1. 1. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China
    2. Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province, Lanzhou 730070, China;
  • Received: Revised: Online: Published:
  • Contact: Shuhui Huo, Xiaoquan Lu
  • About author:
    ** Corresponding author e-mail: (Shuhui Huo);
    (Xiaoquan Lu)
  • Supported by:
    The work was supported by the National Natural Science Foundation of China(21305112); The Natural Science Foundation of Gansu Province(18JR3RA085); The Research Projects of Gansu Universities(2015A-027)
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Food safety has received great attention due to its close connectivity with people’s health and the harmonious development of national economy and society. Trace amount of toxic and harmful compounds in food and water are potentially harmful to human health. Excellent adsorbent and efficient extraction have received more and more attention in food safety detection. Metal-organic frameworks (MOFs) are an emerging class of porous functional materials with high porosity, large surface area, easy structural design, adjustable pore size, as well as acceptable chemical and thermal stability. In the past, the research on MOFs mainly focused on the structural design. Recently, more and more attention has been focused on applications of MOFs in food safety analysis. Meanwhile, their high porosity, tunable surface functionalities, various metal and ligands, as well as diverse coordination modes make MOFs promising as adsorption material for SPE. The merits of MOFs and their functional materials, in particular, are high enrichment, excellent matrix interference resistance, good selectivity, and environmentally-friendly development. Interesting research of MOFs and their functional materials in the pretreatment of food and water samples are summarized.

Key words: metal-organic frameworks, functional materials, sample pretreatment, food safety analysis
Table 1 SPE for the detection of trace heavy metal in food samples[40,41,42,43,44,45,46,47,48,49,50,51]
MOFs Analyte Mode Samples LOD (μg·L-1) Recovery (%) ref
Cu3(BTC)2 Cd(Ⅱ), Pb(Ⅱ), Ni(Ⅱ), Zn(Ⅱ) MSPE-FAAS tap, river, mineral and seawater. soil, sediment and fish extracts 0.12~1.2 88.0~104.0 40
Cu3(BTC)2 Cd(Ⅱ), Zn(Ⅱ), Pb(Ⅱ) MSPE-FAAS baby food 25 93.0~106.0 41
Cu3(BTC)2 Cd(Ⅱ), Pb(Ⅱ), Zn(Ⅱ), Cr(Ⅲ) MSPE-FAAS vegetable 0.12~0.7 92.5~106.0 42
Cu3(BTC)2 Cd(Ⅱ), Pb(Ⅱ), and Ni(Ⅱ) MSPE-FAAS sea food and agri food 0.15~0.8 94.6~102.2 43
Cu3(BTC)2 Hg(Ⅱ) MSPE-CVAAS fish and canned tuna 0.06~60 95.1~102.0 44
MIL-101(Fe) Cd(Ⅱ), Pb(Ⅱ), Zn(Ⅱ), Cr(Ⅲ) MSPE-FAAS agricultural (leek, radish, basil) after microwave digestion 0.15~0.8 87.3~110 45
MIL-101(Fe) Cd(Ⅱ), Pb(Ⅱ), Co(Ⅱ), Ni(Ⅱ), MSPE-FAAS fish 0.13~0.5 88.8~108.0 46
TMU-8 Co(Ⅱ), Cu(Ⅱ), Pb(Ⅱ), Cd(Ⅱ), Ni(Ⅱ), Cr(Ⅲ), Mn(Ⅱ) MSPE-FI-ICP-AES fruit samples and tea 0.3~1 91.0~108.0 47
MOF-199 As(III)and As(V) MSPE-ETAAS rice and canned tuna 1.2 84.0~103.0 48
JUC-62 Hg(Ⅱ) SPE-AFS tea and mushroom 0.40 90.0~93.3 49
PCN-222/
MOF-545		 Hg(Ⅱ) Pipette-Tip SPE-CVAAS fish 0.020 74.3~98.7 50
MOF-545 Pb(Ⅱ) vortex assisted SPE-FAAS cereal, beverage and water 1.78 92~107 51
Fig.1 (a) A schematic diagram of dithizone functionalized Fe3O4synthesis. (b) The schematic illustration of synthesis of magnetic MOF-DHz nanocomposite[40]
Fig.2 Molecular representations of PCN-222/MOF-545[50]
Table 2 SPE for the detection of antibiotics and hormones in food samples[52,53,54,55]
MOF Analyte Mode Samples LOD
(μg·L-1)		 Recovery (%) ref
MIL-101(Cr), MIL-100(Cr), MIL-100 (Fe), MIL-100(Al), UIO-66(Zr), MIL-88B(Cr) penicillin SPME- CEC-UV PENG, PENV, OXA, CLOX, NAFC and DICL 1.2~4.5 63~96.2 52
MIL-53 (Al) penicillin SPME- nano Acquity UPLC river water and milk 0.06~0.26 80.8~90.9 53
MOF-5 estrogens SPME- HPLC milk 0.17~0.31 73.1~80.6 54
MOF-5 chloramphenicol,
thiamphenicol		 SPME- GC-FID milk, honey, urine and serum 0.0148~0.0195 82.3~103.2 55
Table 3 SPE for the detection of pesticides in food samples[58,59,60,61]
MOF Analyte Mode Samples LOD Recovery (%) ref
MIL-101(Cr) herbicides DSPE- HPLC peanuts 0.98~1.9 ng·g-1 89.5~102.7 58
ZIF-8 benzoylurea insecticides DSPE- HPLC water and tangerine 0.10~0.23 ng mL-1 91.7~107.9 59
MIL-101(Cr) amphenicols and their
metabolites		 vortex assisted D-μ-SPE- UPLC-MS / MS aquaculture water 0.05~0.15 ng mL-1 70.1~109.2 60
UiO-66-NH2 Chlorophenoxy acids
herbicides		 D-μ-SPE- HPLC vegetables 0.16~0.37 ng·g-1 82.3~102.0 61
Fig.3 Procedures of the preparation of MOF-C (A) and dispersive solid-phase extraction for benzoylurea insecticides (B)[59]
Table 4 SPE for the detection of persistent organic pollutants in food and water samples[63,64,65,66,67,68,69]
MOF Analyte Mode Samples LOD Recovery (%) ref
MOF-5(Fe) PCBs SBSE-GC-MS fish 0.061~0.096 ng·g-1 94.3~97.5 63
MOF-5 PCBs Aptamer-functionalized
SBSE-GC-MS		 fish 3.0~4.0 ng·L-1 89.2~97.1 64
Bio-MOF-1 PAHs SPME-GC-FID water 0.02~5.57 μg·L-1 80.0~115 65
Magnetic MIL-101 PAHs MSPE-GC-FID water 2.8~27.2 ng·L-1 83.6~105 66
Magnetic MIL-100 PAHs MSPE-GC-FID water 4.6~8.9 ng·L-1 88.5~106.6 67
HKUST-1 PAHs M-d-μ-SPE- UHPLC-FD waters and fruit tea infusions 0.8 ng·L-1 75.0~94.0 68
MIL-101 and MOF-5 PAHs MSPE- GC-MS/ MS waters, food and PM2.5 0.03~0.30 ng·L-1 71.2~109.7 69
Fig.4 锈钢纤维丝水热法原位制备SPME双配体MOF bio-MOF-1 涂层[65]
Fig.5 SEM images of (A) stainless steel wire; (B) and (C) bio-MOF-1 SPME fiber. EDS elemental mapping images for bio-MOF-1 SPME fiber (DG)[65]
Fig.6 Schematic diagram for the application of Fe3O4@SiO2-MIL-101 MNPs as sorbent for MSPE[66]
Fig.7 Schematic diagram of pyrolytic in situ magnetization of MIL-100 (A) and analytical procedures for MSPE. (B)[67]
Fig.8 Synthesis of MOF@MON and fabrication of solid-phase microextraction fibers[69]
Fig.9 Scanning electron micrographs of MIL-101(a) and MIL-101@DMIP(b)[72]
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