- Research Article
- Open Access
Determination of carbamazepine in urine and water samples using amino-functionalized metal–organic framework as sorbent
Chemistry Central Journalvolume 12, Article number: 77 (2018)
A stable and porous amino-functionalized zirconium-based metal organic framework (Zr-MOF-NH2) containing missing linker defects was prepared and fully characterized by FTIR, scanning electron microscopy, powder X-ray diffraction, and BET surface area measurement. The Zr-MOF-NH2 was then applied as an adsorbent in pipette-tip solid phase extraction (PT-SPE) of carbamazepine. Important parameters affecting extraction efficiency such as pH, sample volume, type and volume of eluent, amount of adsorbent, and number of aspirating/dispensing cycles for sample solution and eluent solvent were investigated and optimized. The best extraction efficiency was obtained when pH of 100 µL of sample solution was adjusted to 7.5 and 5 mg of the sorbent was used. Eluent solvent was 10 µL methanol. Linear dynamic range was found to be between 0.1 and 50 µg L−1 and limit of detection for 10 measurement of blank solution was 0.05 µg L−1. This extraction method was coupled to HPLC and was successfully employed for the determination of carbamazepine in urine and water samples. The strategy combined the advantages of fast and easy operation of PT-SPE with robustness and large adsorption capacity of Zr-MOF-NH2.
Carbamazepine (CBZ, 5H-dibenzo [b,f] azepine-5-carboxamide) often used as anticonvulsant drug for treatment of epilepsy [1, 2]. Whenever a patient consumes CBZ, about 2–3% of this drug will excrete unchanged through his urine and enters into environmental aquatic ecosystems . Studies confirmed that CBZ can be present in wastewater (up to 6.3 µg L−1) [4,5,6,7], surface water (up to 1.1 µg L−1) [8, 9], and drinking water (around 30 ng L−1) [10, 11]. Biodegradation of CBZ is very difficult in environmental media owing to its low solubility and stability in water. Therefore, several methods including advanced oxidation processes (AOPs), adsorption on various sorbent media have been employed for the removal and extraction of it [1, 2, 12,13,14].
In recent years, some sample preparation techniques such as liquid–liquid extraction (LLE) , dispersive liquid–liquid microextraction (DLLME)  and solid-phase extraction (SPE)  have been used for isolation and extraction of CBZ in complicated matrices. SPE is a prevalent procedure for pre-treatment of various pharmaceutical analytes due to its reproducibility, high recovery and simple operation. Miniaturized SPE has been developed to overcome on the problems raised by conventional SPE processes such as matrix effect, low detection limit, losses of analytes, and environmental problems due to consumption of large amounts of organic solvents.
Pipette-tip solid-phase extraction (PT-SPE) is a convenience, and microscale of SPE method which reduces amount of sorbent and reagents and saves the analysis time [18,19,20]. This technique required several repeated aspirating/dispensing cycles to complete the extraction procedure.
Metal–organic frameworks (MOFs), a new type of 3D crystalline porous materials assembled by metal ions (or clusters) and multi-topic organic ligands, have received significant attention in a wide array of potential applications such as photocatalysis [21, 22], gas storage [23, 24], separation [25, 26], drug delivery [27, 28], deactivation of chemical warfare agents [29, 30], conductivity [31, 32], removal of toxic materials [33, 34], and sensing [35, 36], due to their large porosity, very high surface area, tunable pore dimensions and topologies as well as their physicochemical properties . Their well-ordered porous structures can create a unique microenvironment to enhance adsorption and penetration of guest species inside the frameworks. Zirconium-based metal–organic frameworks (Zr-MOFs) are one of the most promising MOF materials for practical applications, owing to their thermal, mechanical, and chemical stabilities besides their high surface area and low density. Zr-MOF-NH2 is an amino-functionalized Zr-MOF with the idealized chemical formula Zr6O4(OH)4(L)6 (L = 2-aminoterephthalate) and uniform three-dimensional pores structure composed of 2-aminoterepthalate linkers and hexanuclear [Zr6(μ3–O)4(μ3–OH)4]12+ nodes, each connected to 12 carboxylates of the linkers to yield super octahedral and super tetrahedral cages/cavities (Fig. 1a) . Recently, Hupp and Farha have reported a simple and producible procedure for the preparation of the Zr-MOF-NH2, which contains missing-linker defects . The defects can result in the following advantages; (a) more hydroxyl groups and more open zirconium metal sites which could increase analyte binding affinity and selectivity, and (b) large pores and apertures which might lead to enhance substrate transport rates and in some cases selectivity (Fig. 1b). These advantages combined with amino functionality on organic linker (as coordinating and hydrogen-bonding sites via amino group in addition to possibility of the non-covalent interactions between the organic aromatic linker and guest species) could further improve separation performance and selectivity of the MOF [40,41,42,43,44].
Intrigued by the above-mentioned findings, we encouraged to prepare and use the bio inspired sponge, amino-functionalized Zr-MOF, for micro-scale solid phase extraction and determination of the carbamazepine. Several parameters affecting extraction efficiency including pH, type and volume of eluent, volume of sample solution, and amount of sorbent, number of draw/eject of sample solution and eluent solvent type were tested and optimized. Finally, the method was used for the determination of carbamazepine in urine and water samples.
Chemicals and materials
All reagents (analytical grade) were purchased from Sharloa (Spain) and used as received, except HPLC solvents which were of chromatographic grade. All aqueous solutions were prepared using ultra-pure Milli-Q® purification system. 20 µL pipette-tips (Dragon Lab, China) were used as micro columns. Carbamazepine was obtained from Sigma-Aldrich (St. Louis, MO, USA).
Synthesis of Zr-MOF-NH2 sorbent
Zr-MOF-NH2 was synthesized according to the Hupp/Farha method  with minor modifications. In a 25 mL vial, dimethyl formamide (5 mL) and concentrated HCl (2.85 mL, 850 mmol) were added to 0.125 g, (0.54 mmol) of ZrCl4 before being sonicated for 10 min. A mixture of 2-aminoterephthalic acid (0.134 g, 0.75 mmol) and dimethyl formamide (10 mL) were then added to the clear solution and the mixture was sonicated for 20 more minutes. Afterwards, the capped vial was placed in a pre-heated oven at 80 °C for 15 h. After cooling to room temperature, the solid Zr-MOF-NH2 was filtered and washed with dimethyl formamide, and then with ethanol several times. In order to evaporate any solvents, this product was left for several hours under the hood and then was dried under reduced pressure (80 °C, 3 h). The solid Zr-MOF-NH2 was then activated at 120 °C for 12 h under high vacuum prior to measuring N2 isotherms.
Characterization of Zr-MOF-NH2
Fourier-transform infrared spectroscopy (FT-IR) spectra were recorded using a Perkin-Elmer FTIR (USA). Powder X-ray diffraction (PXRD) patterns were recorded on a Philips X’pert diffractometer (Germany) with monochromated Cu Kα radiation (λ = 1.5418 Å) within the range of 1.5° < 2θ < 38°. Samples for scanning electron microscopy (SEM) were sputtered with a layer of Os (5-nm thickness) prior to taking images on a Hitachi S-4800 SEM (Japan) with a 15.0 kV accelerating voltage. BET surface area measurements were made at 77 K with liquid nitrogen on a Micrometrics TriStar 3020 (N2) surface area analyzer (Britain). Zr-MOF-NH2was degassed for 12 h at 120 °C before the measurement under a stream of nitrogen.
Determination of CBZ was performed on an HPLC manufactured by Cecil company (England), equipped with a C18 ACE column (250 × 4.6 mm, 5 μm particle sizes) and a UV detector at wavelength of 210 nm. A mixture of water: acetonitrile (75:25) were used as mobile phase (isocratic elusion). Column was thermostated at room temperature. Injection volume and flow rate were 10 µL and 1 mL min−1, respectively.
CBZ Extraction procedure
5 mg of Zr-MOF-NH2 was transferred to a 20 µL pipette-tip as micro column and attached to 100 µL variables sampler (Isolable, Germany). 100 µL sample solution was then introduced to column and passed over the sorbent and dispensed back to a 1 mL test-tube. The same sample solution was loaded into the micro column for 5 cycles. Adsorbed CBZ was then eluted by 10 µL of methanol in a 1 mL test-tube for 7 cycles, from which, 20 µL was injected to HPLC. Urine sample was collected from a healthy female and stored at − 80 °C and used throughout all experiments. This participant was not using supplements containing CBZ. Before start of the experiments, sample was brought to the room temperature, of which 250 µL was transferred to a canonical centrifuge tube. After addition of 1 mL of 1 M ammonium persulphate, it was heated in a water bath for 60 min at 95 °C. Then, this solution was brought to room temperature and was extracted by means of the suggested procedure. Tap water was obtained from laboratory and sample was filtered through a 0.45 µm Whatman filter paper and spiked with carbamazepine.
Results and discussion
Characterization of adsorbent
Zr-MOF-NH2 was synthesized using 2-amino-terephthalic acid as the linker, zirconium (IV) chloride as the metal source and HCl as the modulator via a common solvothermal method (see the experimental section and Fig. 1). FT-IR spectrum of the Zr-MOF-NH2 shows a broad absorption peak (at about 3433 cm−1) related to the N–H (the asymmetric and symmetric) and O–H stretching modes (Fig. 2). The peak at 1654 cm−1 is assigned to DMF, while the intense doublet at 1572 and 1386 cm−1 are assigned to the asymmetrical and symmetrical stretching modes of the carboxylate groups (two strongly coupled C–O bonds with bond strengths intermediate between C=O and C–O). The strong aromatic C–N stretching band is observed at 1258 cm−1. The observed peaks between 1400 and 1500 cm−1 are ascribed to the C=C in aromatic compound of the organic linker. The peak at 769 cm−1 is assigned to C–C vibrational mode in the aromatic ring (Fig. 2). The powder X-ray diffraction (PXRD) pattern of the as-prepared Zr-MOF-NH2 agreed well with its structure reported in literature and the simulated PXRD pattern of UiO-66 [40,41,42,43]. The main peaks at 2θ = 7.3° and 8.5° are corresponded to the (111) and the (200) crystal planes, respectively (Fig. 3). The PXRD pattern of the Zr-MOF-NH2 is similar to the one described in literature, confirming the crystalline structure of the MOF. All 2θ peaks are in good agreement with that of PXRD patterns of the Zr-MOF parent material and the simulated one (CCDC No. 889529). The peaks at about 2θ = 7.3°, 8.5°, 12°, 17°, 18.6°, 19.1°, and 22.2° with d spacing of 11.9, 10.3, 7.3, 5.1, 4.7, 4.6, and 4.0 Å can be related to the (1 1 1), (2 0 0), (2 2 0), (4 0 0), (3 3 1), (4 2 0), and (6 0 0) reflections. The intensive peaks at 2θ = 7.3° and 8.5° are corresponded to the planes of tetragonal zirconia.
The morphology of the MOF was examined by scanning electron microscopy (SEM) (Fig. 4). Unlike the octahedral crystal shape of Zr-MOF-NH2 obtained by other methods , the SEM images of the nominal MOF showed aggregates of quasi-spherical particles between 100 and 200 nm.
The permanent porosity of Zr-MOF-NH2 was measured via nitrogen adsorption and desorption (Brunauer–Emmett–Teller, BET), indicating the highly accessible surface area of 1105 m2 g−1, and Langmuir surface area of 1319 m2 g−1, with a pore volume of 0.510667 cm3 g−1. Desorption average pore diameter was found to be 1.848 nm, and the average pore hydraulic radius was measured 0.3.787 nm (Fig. 5). The Zr-MOF-NH2 exhibited the type I isotherm which is characteristic of microporous materials.
Optimization of PT-SPE procedure
To achieve the best extraction efficiency, we tried to optimize the conditions influencing the extraction processes as described below. All optimization experiments were performed with 10 µg L−1 of CBZ solution.
Effect of pH
pH is one of the most important factors in solid phase extraction. This factor illustrates how adsorption can be occurred and which form of the analyte (ionic or molecular) was adsorbed by the sorbent. For evaluation of the effect of pH on extraction efficiency, pH of samples was investigated between 4 and 9 and results are depicted in Fig. 6. As can be seen, the best pH value is 7.5 (around neutral pH) which indicates that CBZ adsorbs on Zr-MOF-NH2 by hydrogen bonding between the amino functionality and surface Zr–OH groups of MOF and carbamazepine. Moreover, Lewis acid–base interaction between CBZ and Zr-MOF-NH2 (including the zirconium ions as an open active sites and the free-carboxylate) may enhance adsorption. The increased affinity for CBZ observed in Zr-MOF-NH2 is a result of an increase in missing linker defects in the functionalized framework because of more terminal and sorbate-displaceable node hydroxo and free-carboxylate ligands. It should be noted that neutral pHs, terminal aqua ligands are mainly converted to hydroxo ligands; therefore, each missing linker generates a pair of defects (one on each node), with each defect site containing of a pair of hydroxo ligands bound to a single zirconium ion and a free-carboxylate group. The Zr-MOF with large numbers of defects can results in increasing capacity of CBZ adsorption.
Amount of adsorbent
In the pipette-tip solid phase extraction, the effect of the adsorbent amount is a main factor on extraction efficiency which must be investigated. To get the PT-SPE column more effective and at lowest possible consumption of adsorbent, different amounts of Zr-MOF-NH2 in the range of 2–12 mg were packed into it. As shown in Fig. 7, maximum extraction of CBZ was achieved when the amount of adsorbent increased to 5.0 mg and further increase in Zr-MOF-NH2 loading decrease the extraction and also prolongs the time required for sample passage. The small decrease in extraction efficiency is probably due to the fact that the quantitative desorption of CBZ from the Zr-MOF-NH2 became more difficult when the same amount of eluent solvent is used with the same washing cycles. Therefore, 5.0 mg was employed as packing material in the fallowing studies.
Effect of volume of sample solution
In this regard, different volumes of sample solution (between 30 and 130 µL) were examined for the extraction of carbamazepine. As given in Fig. 8, the highest extraction efficiency was obtained when a volume of 100 µL of the sample solution was used. By increasing the volume of the sample solution, more analytes can be adsorbed on MOF sorbent; however, after a certain point, equilibrium takes place and extraction efficiency becomes constant.
Effect of volume of eluent
In order to achieve a good enrichment factor and the highest extraction efficiency, various volume of methanol, as the eluent, between 5 and 20 µL were examined. CBZ peak area was increased with increasing the volume of eluent up to and 10 µL of methanol and then was decreased because after the optimum point, the analyte may diluted and extraction efficiency decreased (Fig. 9).
Effect of draw/eject of sample solution and eluent
The procedure of aspiration of a solution into pipette tip and dispensed back into the same sample tube is called aspirating/dispensing (or draw/eject) cycles, which a critical factor for PT-SPE extraction. Therefore, the influence of this parameter on the extraction efficiency was examined between 3 and 20 cycles. After 5 cycles, the extraction of CBZ from sample solution was found to be complete. Meanwhile, the best elusion of CBZ from the sorbent was occured at 7 cycles of draw/eject of eluent. In higher number of cycles, the efficiency was decreased, which is probably due to the back extraction of the analyte from adsorbent into the sample solution, causing a decrease in the recovery.
Reusability of the sorbent
To investigate the stability and reusability of the Zr-MOF-NH2 packed micro column, after desorption of CBZ from the adsorbent, the column was washed five cycles with methanol and then five cycles with deionized water. After that, several extraction and elution operation cycles were carried out under the optimized conditions. The result of experiments indicated that the adsorbent could be reused at least for eight times with a decrease of only 5% in extraction recovery. As the powder PXRD patterns of the Zr-MOF-NH2 before and after adsorption shown in the Fig. 3, the crystallinity of the MOF was reserved during the experimental conditions, confirming the stability of the MOF under the experimental conditions.
The adsorption capacity of the Zr-MOF-NH2 was determined by the batch experiments. For this purpose, a standard solution containing 2000 mg L−1 of CBZ was applied. The amount of adsorbed CBZ was calculated by determination of difference between initial and final concentration of CBZ after adsorption. The maximum sorption capacity was defined as the total amount of adsorbed CBZ per gram of the Zr-MOF-NH2. The obtained capacity was found to be 32 mg g−1. High adsorption capacity indicated that large porosity and large surface area of adsorbent.
The analytical performance of the PT-SPE method was evaluated as the results shown in Table 1. Limit of detection (LOD) was obtained based on a signal-to-noise ratio of 3. The linear dynamic range (LDR) was studied by increasing concentration of the standard solution from 0.05 to 200 µg L−1. The repeatability of the method, expressed as relative standard deviation (RSD). Intra-day precision of proposed method was calculated for seven replicates of the standard at 50 µg L−1 concentration of CBZ. Repeatability was obtained 2.5% for 50 µg L−1 of carbamazepine. The calibration curve was obtained by plotting the peak areas of CBZ against its concentration and was linear in the range of 0.1–50 µg L−1 that demonstrated good linearity of proposed method. The correlation coefficient of calibration curve was 0.999.
Determination of carbamazepine in real samples
The proposed PT-SPE technique was successfully used for the determination of CBZ in urine and water sample. As shown in Table 2, recoveries of all spiked levels are adequate; therefore, we can use this method for the analysis of CBZ in complex matrices as urine. The chromatogram of carbamazepine in blank and spiked urine samples are presented in Fig. 10.
Comparison of proposed method with other methods
A comparison of the proposed method with those using different preconcentration techniques for CBZ determination is given in Table 3, which demonstrates the feasibility and reliability of the applied method. Shorter analysis time, lower consumption of the sorbent and sample solution, simplicity of method and lower eluent volume compared to the other SPE methods, were achieved. Also, Zr-MOF-NH2 as sorbent in comparison with other sorbent that mentioned in Table 3 showed high adsorption capacity, more stability and reusability.
A porous amino-functionalized metal organic framework containing missing-linker defects was firstly prepared and then applied for pipette-tip solid phase extraction of a drug, carbamazepine. The total time of analysis, including extraction was less than 12 min. The Zr-MOF-NH2 sorbent was used for at least eight extractions without any significant change in its capacity or repeatability. Only 5 mg of the sorbent was enough for filling the PT. The presence of more open active zirconium sites, more numbers of hydroxyl groups, the large porosity, very high surface area, the amino functionality, and the suitable pore size of the Zr-MOF-NH2 could improve the extraction of CBZ. Moreover, the fast, inexpensive, effective, reliable, applicable and organic solvent-free method can open up new practical applications for MOFs in SPE based analytical techniques.
Beltran A, Marcé RM, Cormack PAG, Borrull F (2009) Synthesis by precipitation polymerisation of molecularly imprinted polymer microspheres for the selective extraction of carbamazepine and oxcarbazepine from human urine. J Chromatogr A 1216(12):2248–2253
Asgari S, Bagheri H, Es-haghi A, AminiTabrizi R (2017) An imprinted interpenetrating polymer network for microextraction in packed syringe of carbamazepine. J Chromatogr A 1491:1–8
McEneff G, Barron L, Kelleher B, Paull B, Quinn B (2013) The determination of pharmaceutical residues in cooked and uncooked marine bivalves using pressurised liquid extraction, solid-phase extraction and liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 405(29):9509–9521
Ternes TA (1998) Occurrence of drugs in German sewage treatment plants and rivers1. Water Res 32(11):3245–3260
Miao XS, Metcalfe CD (2003) Determination of carbamazepine and its metabolites in aqueous samples using liquid chromatography–electrospray tandem mass spectrometry. Anal Chem 75(15):3731–3738
Kosjek T, Andersen HR, Kompare B, Ledin A, Heath E (2009) Fate of carbamazepine during water treatment. Environ Sci Technol 43(16):6256–6261
Miao XS, Yang JJ, Metcalfe CD (2005) Carbamazepine and its metabolites in wastewater and in biosolids in a municipal wastewater treatment plant. Environ Sci Technol 39(19):7469–7475
Andreozzi R, Marotta R, Pinto G, Pollio A (2002) Carbamazepine in water: persistence in the environment, ozonation treatment and preliminary assessment on algal toxicity. Water Res 36(11):2869–2877
Mashayekhi HA, Abroomand-Azar P, Saber-Tehrani M, Husain SW (2010) Rapid determination of carbamazepine in human urine, plasma samples and water using DLLME followed by RP–LC. Chromatographia 71(5–6):517–521
Dai CM, Zhang J, Zhang YL, Zhou XF, Duan YP, Liu SG (2013) Removal of carbamazepine and clofibric acid from water using double templates–molecularly imprinted polymers. Environ Sci Pollut Res 20(8):5492–5501
Zhou XF, Dai CM, Zhang YL, Surampalli RY, Zhang TC (2011) A preliminary study on the occurrence and behavior of carbamazepine (CBZ) in aquatic environment of Yangtze River Delta, China. Environ Monit Assess 173(1):45–53
Prieto A, Schrader S, Bauer C, Möder M (2011) Synthesis of a molecularly imprinted polymer and its application for microextraction by packed sorbent for the determination of fluoroquinolone related compounds in water. Anal Chim Acta 685(2):146–152
C-m Dai, Geissen SU, Zhang YL, Zhang YJ, Zhou XF (2010) Performance evaluation and application of molecularly imprinted polymer for separation of carbamazepine in aqueous solution. J Hazard Mater 184(1–3):156–163
Akpinar I, Yazaydin AO (2017) Rapid and efficient removal of carbamazepine from water by UiO-67. Ind Eng Chem Res. https://doi.org/10.1021/acs.iecr.7b03208
Teng XW, Wang SWJ, Davies NM (2003) Stereospecific high-performance liquid chromatographic analysis of ibuprofen in rat serum. J Chromatogr B 796(2):225–231
Behbahani M, Najafi F, Bagheri S, Bojdi MK, Salarian M, Bagheri A (2013) Application of surfactant assisted dispersive liquid–liquid microextraction as an efficient sample treatment technique for preconcentration and trace detection of zonisamide and carbamazepine in urine and plasma samples. J Chromatogr A 1308:25–31
Beltran A, Caro E, Marcé RM, Cormack PAG, Sherrington DC, Borrull F (2007) Synthesis and application of a carbamazepine-imprinted polymer for solid-phase extraction from urine and wastewater. Anal Chim Acta 597(1):6–11
Rezaei Kahkha MR, Daliran S, Oveisi AR, Kaykhaii M, Sepehri Z (2017) The mesoporous porphyrinic zirconium metal-organic framework for pipette-tip solid-phase extraction of mercury from fish samples followed by cold vapor atomic absorption spectrometric determination. Food Anal Methods 10(7):2175–2184
Rezaei Kahkha MR, Kaykhaii M, Afarani MS, Sepehri Z (2016) Determination of mefenamic acid in urine and pharmaceutical samples by HPLC after pipette-tip solid phase microextraction using zinc sulfide modified carbon nanotubes. Anal Methods 8(30):5978–5983
Kaykhaii M, Yahyavi H, Hashemi M, Khoshroo MR (2016) A simple graphene-based pipette tip solid-phase extraction of malondialdehyde from human plasma and its determination by spectrofluorometry. Anal Bioanal Chem 408(18):4907–4915
Dhakshinamoorthy A, Asiri AM, García H (2016) Metal-organic framework (MOF) compounds: photocatalysts for redox reactions and solar fuel production. Angew Chem Int Ed 55(18):5414–5445
Aguado S, El-Jamal S, Meunier F, Canivet J, Farrusseng D (2016) A Pt/Al2O3-supported metal-organic framework film as the size-selective core-shell hydrogenation catalyst. Chem Commun 52(44):7161–7163
Mason JA, Veenstra M, Long JR (2014) Evaluating metal-organic frameworks for natural gas storage. Chem Sci 5(1):32–51
Farha OK, Özgür Yazaydın A, Eryazici I, Malliakas CD, Hauser BG, Kanatzidis MG et al (2010) De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities. Nat Chem 2(11):944–948
Navarro-Sánchez J, Argente-García AI, Moliner-Martínez Y, Roca-Sanjuán D, Antypov D, Campíns-Falcó P et al (2017) Peptide metal-organic frameworks for enantioselective separation of chiral drugs. J Am Chem Soc 139(12):4294–4297
Bao Z, Chang G, Xing H, Krishna R, Ren Q, Chen B (2016) Potential of microporous metal-organic frameworks for separation of hydrocarbon mixtures. Energy Environ Sci 9(12):3612–3641
Cunha D, Ben Yahia M, Hall S, Miller SR, Chevreau H, Elkaïm E et al (2013) Rationale of drug encapsulation and release from biocompatible porous metal-organic frameworks. Chem Mater 25(14):2767–2776
Wu MX, Yang YW (2017) Metal–organic framework (MOF)-based drug/cargo delivery and cancer therapy. Adv Mater. https://doi.org/10.1002/adma.201606134
Li P, Moon S-Y, Guelta MA, Lin L, Gómez-Gualdrón DA, Snurr RQ et al (2016) Nanosizing a metal-organic framework enzyme carrier for accelerating nerve agent hydrolysis. ACS Nano 10(10):9174–9182
Bobbitt NS, Mendonca ML, Howarth AJ, Islamoglu T, Hupp JT, Farha OK et al (2017) Metal-organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents. Chem Soc Rev. https://doi.org/10.1039/c7cs00108h
Wang TC, Hod I, Audu CO, Vermeulen NA, Nguyen ST, Farha OK et al (2017) Rendering high surface area, mesoporous metal-organic frameworks electronically conductive. ACS Appl Mater Interfaces 9(14):12584–12591
Zhang FM, Dong LZ, Qin JS, Guan W, Liu J, Li SL et al (2017) Effect of imidazole arrangements on proton-conductivity in metal-organic frameworks. J Am Chem Soc 139(17):6183–6189
Moghadam PZ, Fairen-Jimenez D, Snurr RQ (2016) Efficient identification of hydrophobic MOFs: application in the capture of toxic industrial chemicals. J Mater Chem A 4(2):529–536
Peterson GW, Mahle JJ, DeCoste JB, Gordon WO, Rossin JA (2016) Extraordinary NO2 removal by the metal-organic framework UiO-66-NH2. Angew Chem Int Ed 55(21):6235–6238
Lustig WP, Mukherjee S, Rudd ND, Desai AV, Li J, Ghosh SK (2017) Metal-organic frameworks: functional luminescent and photonic materials for sensing applications. Chem Soc Rev. https://doi.org/10.1039/c6cs00930a
Kreno LE, Leong K, Farha OK, Allendorf M, Van Duyne RP, Hupp JT (2012) Metal-Organic Framework Materials as Chemical Sensors. Chem Rev 112(2):1105–1125
Long JR, Yaghi OM (2009) The pervasive chemistry of metal–organic frameworks. Chem Soc Rev 38(5):1213–1214
Khan NA, Hasan Z, Jhung SH (2013) Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): a review. J Hazard Mater 244:444–456
Katz MJ, Mondloch JE, Totten RK, Park JK, Nguyen ST, Farha OK et al (2014) Simple and compelling biomimetic metal–organic framework catalyst for the degradation of nerve agent simulants. Angew Chem Int Ed 53(2):497–501
Azarifar D, Ghorbani-Vaghei R, Daliran S, Oveisi AR (2017) A multifunctional zirconium-based metal–organic framework for the one-pot tandem photooxidative passerini three-component reaction of alcohols. ChemCatChem. https://doi.org/10.1002/cctc.201700169
Ghorbani-Vaghei R, Davood A, Daliran S, Oveisi AR (2016) The UiO-66-SO3H metal-organic framework as a green catalyst for the facile synthesis of dihydro-2-oxypyrrole derivatives. RSC Adv 6(35):29182–29189
Katz MJ, Brown ZJ, Colon YJ, Siu PW, Scheidt KA, Snurr RQ et al (2013) A facile synthesis of UiO-66, UiO-67 and their derivatives. Chem Commun 49(82):9449–9451
Cavka JH, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S et al (2008) A New zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J Am Chem Soc 130:13850–13851
Schaate A, Roy P, Godt A, Lippke J, Waltz F, Wiebcke M et al (2011) Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals. Chem Eur J 17(24):6643–6651
Queiroz RHC, Bertucci C, Malfará WR, Dreossi SAC, Chaves AR, Valério DAR et al (2008) Quantification of carbamazepine, carbamazepine-10, 11-epoxide, phenytoin and phenobarbital in plasma samples by stir bar-sorptive extraction and liquid chromatography. J Pharm Biomed Anal 48(2):428–434
Zhang J, Liu D, Meng X, Shi Y, Wang R, Xiao D et al (2017) Solid phase extraction based on porous magnetic graphene oxide/β-cyclodextrine composite coupled with high performance liquid chromatography for determination of antiepileptic drugs in plasma samples. J Chromatogr A 1524:49–56
Yu Y, Wu L (2013) Application of graphene for the analysis of pharmaceuticals and personal care products in wastewater. Anal Bioanal Chem 405(14):4913–4919
Ghoraba Z, Aibaghi B, Soleymanpour A (2017) Application of cation-modified sulfur nanoparticles as an efficient sorbent for separation and preconcentration of carbamazepine in biological and pharmaceutical samples prior to its determination by high-performance liquid chromatography. J Chromatogr B 1063:245–252
Mandrioli R, Albani F, Casamenti G, Sabbioni C, Raggi MA (2001) Simultaneous high-performance liquid chromatography determination of carbamazepine and five of its metabolites in plasma of epileptic patients. J Chromatogr B Biomed Sci Appl 762(2):109–116
MRRK did the practical work and wrote the manuscript. Both ARO and BRK co-wrote the manuscript and ARO also synthesized MOF. MK co-wrote the manuscript and planned the study. All authors read and approved the final manuscript.
Authors hereby thanks from health laboratory of Zabol University of Medical Sciences for cooperation to perform experiments.
The authors have declared no competing interests.
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