Metal–Organic Frameworks as Key Materials for Solid-Phase Microextraction Devices—A Review
Abstract
:1. Overview on Metal–Organic Framework
2. Metal–Organic Frameworks in Analytical Separations
3. MOFs in On-Fiber Solid-Phase Microextraction (f-SPME)
3.1. Overwiev on Commercial f-SPME Devices
3.2. Preparation of MOF-Based f-SPME Devices
3.3. Analytical Performance of MOF-Based f-SPME Devices
4. MOFs in On-Arrow-Fiber Solid-Phase Microextraction (af-SPME)
5. MOFs in In-Tube Solid-Phase Microextraction (it-SPME)
6. MOFs in Thin-Film Solid-Phase Microextraction (tf-SPME)
7. MOFs in Stir-Bar (sb-SPME) and Stir-Cake Solid-Phase Microextraction (sc-SPME)
8. Comparison with Other MOF-Based Extraction Methods
9. Concluding Remarks
Funding
Acknowledgments
Conflicts of Interest
Abbreviations
af-SPME | arrow fiber solid-phase microextraction |
ALD | atomic layer deposition |
BMA-EDMA | butyl methacrylate-ethylene dimethacrylate |
CE | capillary electrophoresis |
CEC | capillary electrochromatography |
d-µ-SPE | dispersive solid-phase microextraction |
DAD | diode array detection |
DI | direct immersion |
ECD | electron capture detection |
f-SPME | on-fiber solid-phase microextraction |
FID | flame ionization detection |
GC | gas chromatography |
FPD | flame photometric detection |
HS | headspace |
IL | ionic liquid |
IRMOF | isoreticular metal–organic framework |
it-SPME | in-tube solid-phase microextraction |
LC | liquid chromatography |
LOD | limit of detection |
m-d-µ-SPE | magnetic-assisted miniaturized solid-phase extraction |
MIP | molecularly imprinted polymer |
MNP | magnetic nanoparticle |
MOF | metal–organic framework |
MS | mass spectrometry |
MS/MS | tandem mass spectrometry |
OCP | organochlorine pesticide |
OPP | organophosphorus pesticide |
PAH | polycyclic aromatic hydrocarbon |
PAN | polyacrylonitrile |
PCB | polychlorinated biphenyl |
PDMS | polydimethylsiloxane |
PEEK | polyetheretherketone |
PS | polystyrene |
PVC | polyvinylchloride |
PVDF | polyvinylidene difluoride |
sb-SPME | stir-bar solid-phase microextraction |
SBU | secondary building unit |
sc-SPME | stir-cake solid-phase microextraction |
SESI | secondary electrospray ionization |
SPME | solid-phase microextraction |
tf-SPME | thin-film solid-phase microextraction |
µ-SPE | miniaturized solid-phase extraction |
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MOF | Support | Additive* | Size (Length/Diameter/Thickness) | Preparation Method | Sample/Analyte* (Number) | Analytical Method* | Extraction Time (min) | RSDmax/RSDbatch a | Ref. |
---|---|---|---|---|---|---|---|---|---|
On-fiber solid-phase microextraction (f-SPME) | |||||||||
HKUST-1(Cu) | stainless steel wire | – | –/–/40 µm | in-situ growth | indoor air/benzene derivatives (7) | HS mode and GC-FID | 20 | 7.7/9.4 | [61] |
UiO-66(Zr) | fused silica fiber | – | –/–/25 µm | in-situ growth | water and soil/PAHs (10) | DI mode and GC-MS | 20 | 8.2/8.9 | [62] |
ZIF-90(Zn) | stainless steel wire | – | –/–/30.5 µm | in-situ growth | water, soil, and vegetables/PCBs (6) | DI mode and GC-MS | 40 | 5.5/9.1 | [63] |
E-MOF-5(Zn) | stainless steel wire | – | –/–/12.5 µm | electro-deposition | milk/hormones (4) | DI mode and LC-DAD | 30 | 9.4/6.1 | [64] |
HKUST-1(Cu) | fused silica fiber | graphite oxide | –/–/40 µm | immersion in the composite | water and soil/OCPs (8) | HS mode and GC-ECD | 40 | 8.8/12.8 | [65] |
MIL-53(Al) | stainless steel wire | epoxy glue as adhesive | –/–/50 µm | attachment with adhesive | water/PAHs (16) | HS mode and GC-MS/MS | 50 | 12.5/13.9 | [66] |
UiO-66(Zr) | stainless steel wire | epoxy glue as adhesive | –/–/150 µm | attachment with adhesive | water/phenols (6) | HS mode and GC-FID | 50 | 6.2/10.1 | [67] |
MIL-101-NH2(Cr) | quartz | PAN as adhesive | –/–/120 µm | attachment with adhesive | fish/antibiotics (6) | In-vivo and LC-MS/MS | 10 | 6.8/9.5 | [68] |
MIL-101(Cr) | stainless steel wire | PDMS | –/–/70 µm | sol–gel | water/PAHs (5) | HS mode and GC-MS | 20 | 9.3/13.8 | [69] |
ZIF-8(Zn) | fiber bundle with 4 monoliths | graphene oxide and MIP | 3 cm/0.35 cm/– | mold polymerization | food/hormones (5) | DI mode and LC-MS | 30 | 4.1/5.2 | [70] |
On-arrow-fiber solid-phase microextraction (af-SPME) | |||||||||
ZIF-8(Zn) | arrow steel rod | PVC as adhesive | 2 cm/–/70 µm | attachment with adhesive | wastewater, fish and mushroom/amines (2) | HS mode and GC-MS | 5 | 10.3/15.6 | [51] |
Fe-BDC(Fe) | arrow steel rod | - | 2 cm/–/2 µm | atomic layer deposition and conversion | wastewater/chloro-phenols (8) | HS mode and GC-MS | 30 | 23.1/– | [71] |
In-tube solid-phase microextraction (it-SPME) | |||||||||
MIL-101(Cr) | capillary tube | BMA-EDMA and IL [C6mim][BF4] | 10 cm/0.8 mm/– | microwave assisted polymerization | water/drugs (6) | CEC-UV-Vis | 34 | 5.2/– | [72] |
MIL-53(Al) | capillary tube | BMA-EDMA and IL [C6mim][BF4] | 10 cm/0.8 mm/– | microwave assisted polymerization | water/sulfonamides (7) | CE-UV-Vis | 36 | 6.4/5.3 | [49] |
MOF | Support | Additive* | Size (Length/Diameter/Thickness) | Preparation Method | Sample/Analyte* (Number) | Analytical Method* | Extraction Time (min) | RSDmax/RSDbatch a | Ref. |
Thin film solid-phase microextraction (tf-SPME) | |||||||||
MIL-53(Al) | – | PVDF | 2 cm/–/– | spreading | urine/estrogens (4) | LC-FD | 45 | 11.4/– | [50] |
Stir-bar solid-phase microextraction (sb-SPME) | |||||||||
IRMOF-3(Zn) | capillary glass bar | PDMS | 2 cm/–/100 µm | sol–gel | water/estrogens (7) | LC-UV | 55 | 10.2/16.1 | [73] |
MIL-53-NH2(Al) | capillary glass bar | PDMS | 2 cm/–/125 µm | sol–gel | water/PAHs (15) | LC-FD | 30 | 11.7/16.9 | [74] |
MOF-5(Fe) | Nd-Fe-B rod | MNP Fe3O4@NH2 | 1 cm/–/– | magnetic interaction | fish/PCBs (6) | GC-MS | 33 | 4.3/– | [75] |
MIL-101-NH2(Cr) | capillary glass bar | PDMS | 2 cm/–/100 µm | sol–gel | water/OPPs (6) | GC-FPD | 35 | 10.7/9.2 | [48] |
UiO-66-NH2(Zr) | – | Nd-Fe-B powder, 4-VP | 2 cm/30 mm/– | thermal polymerization | soil and water/herbicides (5) | LC-UV | 60 | 13.8/9.5 | [76] |
Extraction Method* | MOF | Amount of Sorbent a | Volume of Sample | Desorption | Additional Steps | Extraction Time | Reuse of the Sorbent/Device | Analytical Technique* | LOD (ng·L−1) | Ref. |
---|---|---|---|---|---|---|---|---|---|---|
Analytical application 1: determination of pesticides in waters | ||||||||||
µ-dSPE | UiO-66(Zr) | 40 mg | 5 mL | liquid (1 mL acetone) | centrifugation, evaporation and reconstitution | ~20 min | 10 times | LC-MS/MS | 20–400 | [144] |
m-µ-dSPE | ZIF-8(Zn) | 0.5 mg | 10 mL | liquid (1 mL methanol) | evaporation and reconstitution | ~45 min | No | LC-MS/MS | 0.19–1.20 | [145] |
f-SPME (HS mode) | HKUST-1(Cu) | – × 40 µm | 25 mL | thermal (280 °C) | – | ~45 min | 140 times | GC-ECD | 2.8–6.9 | [65] |
tf-SPME | ZIF-67(Zn) | 1 cm × 80 µm | 15 mL | thermal (220 °C) | – | ~22 min | No | SESI/MS | 100 | [129] |
sb-SPME | MIL-101-NH2(Cr) | 2 cm × 100 µm | 10 mL | liquid (50 µL acetone) | – | ~35 min | 50 times | GC-FPD | 43–85 | [48] |
Analytical application 2: determination of drugs in waters | ||||||||||
µ-SPE | MIL-101(Cr) | 40 mg | 60 mL | liquid (4 mL methanol) | evaporation and reconstitution | ~60 min | No | LC-MS/MS | 30–80 | [146] |
m-µ-dSPE | MIL-101(Cr) | 30 mg | 50 mL | liquid (200 µL acetonitrile) | evaporation and reconstitution | ~30 min | No | LC-MS/MS | 3–60 | [147] |
f-SPME (HS mode) | HKUST-1(Cu) | 1 cm × 30 µm | 5 mL | liquid (2 mL acetonitrile:H2O 1:1) | evaporation and reconstitution | ~60 min | 110 times | LC-UV-Vis | 30–50 | [78] |
it-SPME | MIL-101(Cr) | 3 cm × – | 2 mL | liquid (200 µL methanol) | – | ~35 min | 45 times | CEC-UV-Vis | 1200–4500 | [72] |
sb-SPME | MIL-101(Cr) | 1 cm × – | 10 mL | liquid (1 mL acetonitrile) | evaporation and reconstitution | ~80 min | 4 times | LC-MS/MS | 11–35 | [141] |
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Gutiérrez-Serpa, A.; Pacheco-Fernández, I.; Pasán, J.; Pino, V. Metal–Organic Frameworks as Key Materials for Solid-Phase Microextraction Devices—A Review. Separations 2019, 6, 47. https://doi.org/10.3390/separations6040047
Gutiérrez-Serpa A, Pacheco-Fernández I, Pasán J, Pino V. Metal–Organic Frameworks as Key Materials for Solid-Phase Microextraction Devices—A Review. Separations. 2019; 6(4):47. https://doi.org/10.3390/separations6040047
Chicago/Turabian StyleGutiérrez-Serpa, Adrián, Idaira Pacheco-Fernández, Jorge Pasán, and Verónica Pino. 2019. "Metal–Organic Frameworks as Key Materials for Solid-Phase Microextraction Devices—A Review" Separations 6, no. 4: 47. https://doi.org/10.3390/separations6040047