Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants

Four metal-organic frameworks (MOFs), specifically UiO-66, UiO-66-NH2, UiO-66-NO2, and MIL-53(Al), were synthesized, characterized, and used as sorbents in a dispersive micro-solid phase extraction (D-µSPE) method for the determination of nine pollutants of different nature, including drugs, phenols, polycyclic aromatic hydrocarbons, and personal care products in environmental waters. The D-µSPE method, using these MOFs as sorbents and in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD), was optimized. The optimization study pointed out to UiO-66-NO2 as the best MOF to use in the multi-component determination. Furthermore, the utilization of isoreticular MOFs based on UiO-66 with the same topology but different functional groups, and MIL-53(Al) to compare with, allowed us for the first time to evaluate the influence of such functionalization of the ligand with regards to the efficiency of the D-µSPE-HPLC-DAD method. Optimum conditions included: 20 mg of UiO-66-NO2 MOF in 20 mL of the aqueous sample, 3 min of agitation by vortex and 5 min of centrifugation, followed by the use of only 500 µL of acetonitrile as desorption solvent (once the MOF containing analytes was separated), 5 min of vortex and 5 min of centrifugation. The validation of the D-µSPE-HPLC-DAD method showed limits of detection down to 1.5 ng·L−1, average relative recoveries of 107% for a spiked level of 1.50 µg·L−1, and inter-day precision values with relative standard deviations lower than 14%, for the group of pollutants considered.

Download Full-text

Mixed Functionalization of Organic Ligands in UiO-66: A Tool to Design Metal–Organic Frameworks for Tailored Microextraction

Molecules ◽

10.3390/molecules24203656 ◽

2019 ◽

Vol 24 (20) ◽

pp. 3656 ◽

Cited By ~ 5

Author(s):

Gabriel González-Rodríguez ◽

Iván Taima-Mancera ◽

Ana B. Lago ◽

Juan H. Ayala ◽

Jorge Pasán ◽

...

Keyword(s):

High Performance ◽

Solid Phase ◽

Metal Organic Framework ◽

X Ray Diffraction ◽

X Ray ◽

Polar Groups ◽

Polycyclic Aromatic ◽

Metal Organic ◽

Array Detection

The mixed-ligand strategy was selected as an approach to tailor a metal–organic framework (MOF) with microextraction purposes. The strategy led to the synthesis of up to twelve UiO-66-based MOFs with different amounts of functionalized terephthalate ligands (H-bdc), including nitro (-NO2) and amino (-NH2) groups (NO2-bdc and NH2-bdc, respectively). Increases of 25% in ligands were used in each case, and different pore environments were thus obtained in the resulting crystals. Characterization of MOFs includes powder X-ray diffraction, infrared spectroscopy, and elemental analysis. The obtained MOFs with different degrees and natures of functionalization were tested as sorbents in a dispersive miniaturized solid-phase extraction (D-µSPE) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD), to evaluate the influence of mixed functionalization of the MOF on the analytical performance of the entire microextraction method. Eight organic pollutants of different natures were studied, using a concentration level of 5 µg· L−1 to mimic contaminated waters. Target pollutants included carbamazepine, 4-cumylphenol, benzophenone-3, 4-tert-octylphenol, 4-octylphenol, chrysene, indeno(1,2,3-cd)pyrene, and triclosan, as representatives of drugs, phenols, polycyclic aromatic hydrocarbons, and disinfectants. Structurally, they differ in size and some of them present polar groups able to form H-bond interactions, either as donors (-NH2) or acceptors (-NO2), permitting us to evaluate possible interactions between MOF pore functionalities and analytes’ groups. As a result, extraction efficiencies can reach values of up to 60%, despite employing a microextraction approach, with four main trends of behavior being observed, depending on the analyte and the MOF.

Download Full-text

Application of a Pillared-Layer Zn-Triazolate Metal-Organic Framework in the Dispersive Miniaturized Solid-Phase Extraction of Personal Care Products from Wastewater Samples

Molecules ◽

10.3390/molecules24040690 ◽

2019 ◽

Vol 24 (4) ◽

pp. 690 ◽

Cited By ~ 8

Author(s):

Providencia González-Hernández ◽

Ana Lago ◽

Jorge Pasán ◽

Catalina Ruiz-Pérez ◽

Juan Ayala ◽

...

Keyword(s):

Solid Phase Extraction ◽

Solid Phase ◽

Metal Organic Framework ◽

Personal Care Products ◽

Aqueous Sample ◽

Phase Extraction ◽

Personal Care ◽

Relative Standard ◽

Metal Organic ◽

Organic Framework

The pillared-layer Zn-triazolate metal-organic framework (CIM-81) was synthesized, characterized, and used for the first time as a sorbent in a dispersive micro-solid phase extraction method. The method involves the determination of a variety of personal care products in wastewaters, including four preservatives, four UV-filters, and one disinfectant, in combination with ultra-high performance liquid chromatography and UV detection. The CIM-81 MOF, constructed with an interesting mixed-ligand synthetic strategy, demonstrated a better extraction performance than other widely used MOFs in D-µSPE such as UiO-66, HKUST-1, and MIL-53(Al). The optimization of the method included a screening design followed by a Doehlert design. Optimum conditions required 10 mg of CIM-81 MOF in 10 mL of the aqueous sample at a pH of 5, 1 min of agitation by vortex and 3 min of centrifugation in the extraction step; and 1.2 mL of methanol and 4 min of vortex in the desorption step, followed by filtration, evaporation and reconstitution with 100 µL of the initial chromatographic mobile phase. The entire D-µSPE-UHPLC-UV method presented limits of detection down to 0.5 ng·mL−1; intra-day and inter-day precision values for the lowest concentration level (15 ng·mL−1)-as a relative standard deviation (in %)-lower than 8.7 and 13%, respectively; average relative recovery values of 115%; and enrichment factors ranging from ~3.6 to ~34. The reuse of the CIM-81 material was assessed not only in terms of maintaining the analytical performance but also in terms of its crystalline stability.

Download Full-text

Polydimethylsiloxane/metal-organic frameworks coated fiber for solid-phase microextraction of polycyclic aromatic hydrocarbons in river and lake water samples

Talanta ◽

10.1016/j.talanta.2014.06.013 ◽

2014 ◽

Vol 129 ◽

pp. 600-605 ◽

Cited By ~ 71

Author(s):

Guijiang Zhang ◽

Xiaohuan Zang ◽

Zhi Li ◽

Chun Wang ◽

Zhi Wang

Keyword(s):

Polycyclic Aromatic Hydrocarbons ◽

Aromatic Hydrocarbons ◽

Lake Water ◽

Water Samples ◽

Solid Phase Microextraction ◽

Solid Phase ◽

Metal Organic Frameworks ◽

Coated Fiber ◽

Polycyclic Aromatic ◽

Metal Organic

Download Full-text

Structure- and porosity-tunable, thermally reactive metal organic frameworks for high-performance Ni-rich layered oxide cathode materials with multi-scale pores

Journal of Materials Chemistry A ◽

10.1039/c9ta02462j ◽

2019 ◽

Vol 7 (25) ◽

pp. 15190-15197

Author(s):

Jun-Ho Park ◽

Kwangjin Park ◽

Dongwook Han ◽

Dong-Hee Yeon ◽

Heechul Jung ◽

...

Keyword(s):

Cathode Materials ◽

High Performance ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

Reactive Metal ◽

Layered Oxide ◽

Multi Scale ◽

Oxide Cathode ◽

Metal Organic ◽

First Time

We describe for the first time molecular rearrangements in a highly stable and porous Ni-rich layered oxide cathode material (LiNi0.80Co0.15Mn0.05O2, Ni-rich NCM) using a thermally reactive, Co-embedded metal–organic framework (MOF).

Download Full-text

Simultaneous quantifications of four purine derivatives biomarkers in cow milk by SPE HPLC-DAD

Czech Journal of Food Sciences ◽

10.17221/297/2020-cjfs ◽

2021 ◽

Vol 39 (No. 2) ◽

pp. 122-130

Author(s):

Mihaela Vlassa ◽

Miuta FILIP ◽

Catalin DRAGOMIR

Keyword(s):

Uric Acid ◽

High Performance ◽

Solid Phase ◽

Cow Milk ◽

Good Precision ◽

Purine Derivatives ◽

Buffer Solution ◽

Solution Ph ◽

Relative Standard ◽

Array Detection

In this study, simultaneous quantification of allantoin, uric acid, xanthine, and hypoxanthine in cow milk by solid phase extraction (SPE) and high performance liquid chromatography-diode array detection (HPLC-DAD) method was perform. Five different SPE cartridges were tested in order to evaluate the isolation of purine derivatives (PD) from cow milk. Chromatography was carried out on ODS-2 Hypersil column and 0.05 M (NH4)2HPO4 buffer solution (pH = 7.76) as mobile phase. The HPLC-DAD validated method showed a linearity with regression coefficients higher than 0.999 and the limits of detection and quantification with values in the range 0.09–0.74 µg mL–1 and 0.27–2.24 µg mL–1, respectively. The method showed good precision with a relative standard deviation (RSD) below 4.48%, while the accuracy ranged from 95.34 to 104.47% for all analytes. The best recovery degree of PD by SPE were obtained on Strata SCX cartridge for xanthine (87.79%) and hypoxanthine (89.02%); on Strata NH2 for allantoin (35.09%) and on Strata C8 for uric acid (101.08%). Finally, the HPLC-DAD method with SPE on SCX cartridges was applied to quantify the PD in a batch of thirty cow milk samples.

Download Full-text