Abstract
Efficient determination of aldehydes by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is hampered mainly by the low mass and unstable nature of analytes. In the present work, we propose a combined strategy of a reactive metal–organic framework (MOF) matrix for the derivatization and detection of aldehydes. A novel reactive MOF matrix (NH2NH-MOF) was synthesized in two steps. First, NR3+-MOF was synthesized via Cu2+ and the quaternary amine ligand 4,4′-bipyridinium, 1,1″-(1,2-ethanediyl)bis-, dibromide (PyEtBr). Then, -NHNH2 was introduced to NR3+-MOF through electrostatic adsorption between the -NR3+ and -HSO3− of 4-hydrazinylbenzenesulfonic acid to synthesize NH2NH-MOF. The acid–base chemistry of NH2NH-MOF led to uniform cocrystallization of the aldehyde-matrix mixtures and helped to achieve the detection of low-weight aldehydes with good relative standard deviations (RSDs = 0.07–12.35%). It was confirmed that this strategy can accurately quantify formaldehyde, valeraldehyde, and benzaldehyde with good linearity (r > 0.97). Furthermore, this strategy was applied to quantitatively detect benzaldehyde in wastewater, thus showing potential applications in environmental pollutant detection.
Graphical abstract
Similar content being viewed by others
References
Abushareeda W, Lyris E, Kraiem S, Al Wahaibi A, Alyazidi S, Dbes N, Lommen A, Nielen M, Horvatovich PL, Alsayrafi M, Georgakopoulos C (2017) Gas chromatographic quadrupole time-of-flight full scan high resolution mass spectrometric screening of human urine in antidoping analysis. J Chromatogr B 1063:74–83
Alipanahpour DE, Ghaedi M, Asfaramb A (2017) Optimization and modeling of pre-concentration and determination of dyes based on ultrasound assisted-dispersive liquid-liquid microextraction coupled with derivative spectrophotometry. Ultrason Sonochem 34:27–36
Dil EA, Ghaedi M, Asfaram A, Zare F, Mehrabi F, Sadeghfar F (2017) Comparison between dispersive solid-phase and dispersive liquid-liquid micro-extraction combined with spectrophotometric determination of malachite green in water samples based on ultrasound-assisted and preconcentration under multi-variable experimental design optimization. Ultrason Sonochem 39:374–383
Shigeri Y, Yasuda A, Sakai M, Ikeda S, Arakawa R, Sato H, Kinumi T (2015) Hydrazide and hydrazine reagents as reactive matrices for matrix-assisted laser desorption/ionization mass spectrometry to detect steroids with carbonyl groups. Eur J Mass Spectrom 21(2):79–90
Shigeri Y, Yasuda A, Sakai M, Ikeda S, Arakawa R, Sato H, Kinumi T (2016) 2-Hydrazinoquinoline: a reactive matrix for matrix-assisted laser desorption/ionization mass spectrometry to detect gaseous carbonyl compounds. Eur J Mass Spectrom 22(2):83–90
Liu HL, Chang YJ, Fan T, Gu ZY (2016) Two-dimensional metal-organic framework nanosheets as a matrix for laser desorption/ionization of small molecules and monitoring enzymatic reactions at high salt concentrations. Chem Commun 52(88):12984–12987
Monopoli A, Calvano CD, Nacci A, Palmisano F (2014) Boronic acid chemistry in MALDI MS: a step forward in designing a reactive matrix with molecular recognition capabilities. Chem Commun 50(33):4322–4324
Zhao XY, Guo C, Huang Y, Huang LL, Ma G, Liu YQ, He Q, Wang HW, Chen KS, Pan YJ (2019) Combination strategy of reactive and catalytic matrices for qualitative and quantitative profiling of N-glycans in MALDI-MS. Anal Chem 91(14):9251–9258
Ling L, Xiao CS, Ma Y, Jiang LY, Wang S, Guo LM, Jiang SM, Guo XH (2019) 2-Phenyl-3-(p-aminophenyl) acrylonitrile: a reactive matrix for sensitive and selective analysis of glycans by MALDI-MS. Anal Chem 91(14):8801–8807
Lin Z, Cai ZW (2018) Negative ion laser desorption/ionization time-of-flight mass spectrometric analysis of small molecules by using nanostructured substrate as matrices. Mass Spec Rev 37(5):681–696
Lu MH, Yang XQ, Yang YX, Qin PG, Wu XR, Cai ZW (2017) Nanomaterials as assisted matrix of laser desorption/ionization time-of-flight mass spectrometry for the analysis of small molecules. Nanomaterials 7(4):87
Yuan N, Gong XR, Sun WD, Yu CH (2021) Advanced applications of Zr-based MOFs in the removal of water pollutants. Chemosphere 267:128863
Yang J, Yang YW (2020) Metal-organic frameworks for biomedical applications. Small 16(10):1906846
Daglar H, Gulbalkan HC, Avci G, Aksu GO, Altundal OF, Altintas C, Erucar I, Keskin S (2021) Effect of metal-organic framework (MOF) database selection on the assessment of gas storage and separation potentials of MOFs. Angew Chem Int Ed 60(14):7828–7837
Garai M, Yavuz CT (2021) Robust mesoporous Zr-MOF with Pd nanoparticles for formic-acid-based chemical hydrogen storage. Matter 4(1):10–12
Singh C, Mukhopadhyay S, Hod I (2021) Metal-organic framework derived nanomaterials for electrocatalysis: recent developments for CO2 and N2 reduction. Nano Convergence 8(1):1
Amiripour F, Ghasemi S, Azizi SN (2021) Design of turn-on luminescent sensor based on nanostructured molecularly imprinted polymer-coated zirconium metal-organic framework for selective detection of chloramphenicol residues in milk and honey. Food Chem 347:129034
Ma Q, Chu SS, Li H, Guo J, Zhang Q, Lin ZQ, Wang JP, Che QD (2021) Bi-component MOF-derived high-sensitive triethylamine gas sensors based on MoO3/ZnMoO4/CoMoO4 hierarchical structures effectuated by tunable surface/interface transfer behavior. J Mater Sci 56(13):7906–7919
Shih YH, Chien CH, Singco B, Hsu CL, Lin CH, Huang HY (2013) Metal-organic frameworks: new matrices for surface-assisted laser desorption-ionization mass spectrometry. Chem Commun 49(43):4929–4931
Feng D, Xia Y (2018) Covalent organic framework as efficient desorption/ionization matrix for direct detection of small molecules by laser desorption/ionization mass spectrometry. Anal Chim Acta 1014:58–63
Li J, Peng YL, Liu Y, Li WW, Jin Y, Tang ZT, Duan YX (2014) Investigation of potential breath biomarkers for the early diagnosis of breast cancer using gas chromatography-mass spectrometry. Clin Chim Acta 436:59–67
Guadagni R, Miraglia N, Simonelli A, Silvestre A, Lamberti M, Feola D, Acampora A, Sannolo N (2011) Solid-phase microextraction–gas chromatography-mass spectrometry method validation for the determination of endogenous substances: urinary hexylaldehyde and heptanal as lung tumor biomarkers. Anal Chim Acta 701(1):29–36
Abdelhamid HN (2018) Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes. Microchim Acta 185:200
Shi CY, Deng CH (2016) Recent advances in inorganic materials for LDI-MS analysis of small molecules. Analyst 141(10):2816–2826
Kim J (2015) Sample preparation for matrix-assisted laser desorption/ionization mass spectrometry. Mass Spectrom Lett 6:27–30
Alexovic M, Dotsikas Y, Bober P, Sabo J (2018) Achievements in robotic automation of solvent extraction and related approaches for bioanalysis of pharmaceuticals. J Chromatogr B 1092:402–421
Abushareeda W, Vonaparti A, Al Saad K, Almansoori M, Meloug M, Saleh A, Aguilera R, Angelis Y, Horvatovich PL, Lommen A, Alsayrafi M, Georgakopoulos C (2018) High resolution full scan liquid chromatography mass spectrometry comprehensive screening in sports antidoping urine analysis. J Pharm Biomed Anal 151:10–24
Xu M, Yang SS, Gu ZY (2018) Two-dimensional metal-organic framework nanosheets: a rapidly growing class of versatile nanomaterials for gas separation, MALDI-TOF matrix and biomimetic applications. Chem Eur J 24(57):15131–15142
Da HJ, Yang CX, Yan XP (2019) Cationic covalent organic nanosheets for rapid and selective capture of perrhenate: an analogue of radioactive pertechnetate from aqueous solution. Environ Sci Technol 53(9):5212–5220
Wang J, Han PP, Xia Y (2019) A cationic metal-organic framework for the highly efficient removal of thiocyanate from water. Microporous Mesoporous Mater 287:107–113
Hu YN, Chen D, Zhang TY, Ding J, Feng YQ (2020) Use of ammonium sulfite as a post-column derivatization reagent for rapid detection and quantification of aldehydes by LC-MS. Talanta 206:120172
Qiao Z, Perestrelo R, Reyes-Gallardo EM, Lucena R, Cardenas S, Rodrigues J, Camara JS (2015) Octadecyl functionalized core-shell magnetic silica nanoparticle as a powerful nanocomposite sorbent to extract urinary volatile organic metabolites. J Chromatogr A 1393:18–25
Liu JF, Yuan BF, Feng YQ (2015) Determination of hexanal and heptanal in human urine using magnetic solid phase extraction coupled with in-situ derivatization by high performance liquid chromatography. Talanta 136:54–59
Funding
Financial support was obtained from the National Natural Science Foundation of China (21874073) and the NCC Fund (NCC2020PY11).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Highlights
• NH2NH-MOF was synthesized, providing a new reactive matrix that possesses molecular recognition properties.
• Selective recognition of small aldehydes was achieved in complex samples with good accuracy.
• An MOF matrix was developed with built-in recognition capabilities, providing new ideas for the functional expansion of MOFs.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Zheng, R., Yang, Y. & Xia, Y. NH2NH-MOF: a reaction matrix for the specific determination of small aldehydes by MALDI-MS. Microchim Acta 189, 51 (2022). https://doi.org/10.1007/s00604-021-05143-y
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00604-021-05143-y