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ORIGINAL PAPER
Bio-metal-organic frameworks for molecular recognition and sorbent
extraction of hydrophilic vitamins followed by their determination
using HPLC-UV
Héctor Martínez Pérez-Cejuela
1
&Marta Mon
2
&Jesús Ferrando-Soria
2
&Emilio Pardo
2
&
Donatella Armentano
3
&Ernesto F. Simó-Alfonso
1
&José Manuel Herrero-Martínez
1
Received: 27 November 2019 /Accepted: 24 February 2020 /P ublished online: 5 March 2020
#Springer-Verlag GmbH Austria, part of Springer Nature 2020
Abstract
A bio-metal-organic framework (bio-MOF) derived from the amino acid L-serine has been prepared in bulk form and evaluated
as sorbent for the molecular recognition and extraction of B-vitamins. The functional pores of bio-MOF exhibit high amounts of
hydroxyl groups jointly directing other supramolecular host-guest interactions thus providing the recognition of B-vitamins in
fruit juicesand energy drinks. Single-crystal X-ray diffraction studies reveal the specific B-vitamin binding sites and the existence
of multiple hydrogen bonds between these target molecules and the framework. It offered unique snapshots to accomplish an
efficient capture of these solutes in complex aqueous matrices. Four B-vitamins (thiamin, nicotinic acid, nicotinamide, and
pyridoxine) were investigated. They were eluted from the sorbent with phosphate buffer at pH 7 and analyzed by HPLC with
UV detection. The sorbent was compared with commercial C18 cartridges. Following the procedure, acceptable reproducibility
(RSD values <14%) was achieved, and the detection limits were in the range 0.4 to 1.4 ng mL
−1
. The method was applied to the
analysis of energy drink and juice samples and the recoveries were between 75 and 123% in spiked beverage samples.
Keywords Bio-MOF .L-serine .Host-guest interaction .Single-crystal X-ray diffraction .Sample preparation .Solid-phase
extraction .HILIC .Water-soluble vitamins .Functional beverages
Introduction
Metal-organic frameworks (MOFs) are crystalline materials,
which are made up of coordination bonds between
multidentate organic linkers and transition-metal cations into
periodic structures [1,2]. These tailored porous materials have
developed quickly in the last 20 years [3]. They have shown
promising features (e.g., easy preparation, high porosity and
surface areas, large mechanical and good thermal stability,
etc.) for several applications, such as gas storage [4], removal
of pollutants [5,6], and separation and catalysis [7–9]. In
analytical field, these materials have been applied in chro-
matographic area and sample preparation [10,11]. Despite
the remarkable advances in MOFs as stationary phases, most
of them have addressed to solid-phase microextraction
(SPME) purposes [12]. In most cases, the selectivity of sepa-
ration has been attributed to the hydrophobic and π-
interactions of solutes with the functional (commonly aromat-
ic) ligands instead of taking advantages of their tunable pore
size and molecular recognition capabilities.
In 2010, a new subclass of MOFs combining supramolec-
ular chemistry and bioscience has arisen, the so-called biolog-
ical metal-organic frameworks (bio-MOFs) [13]. These
materials have attracted wide attention due to their particular
structures, rich supramolecular chemistry, and unique biomi-
metic properties. These porous materials constructed from
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s00604-020-4185-z) contains supplementary
material, which is available to authorized users.
*Emilio Pardo
emilio.pardo@uv.es
*José Manuel Herrero-Martínez
jmherrer@uv.es
1
Department of Analytical Chemistry, University of Valencia, c/Dr.
Moliner, 50, 46100 Valencia, Burjassot, Spain
2
Department of Inorganic Chemistry, Institute of Molecular Science
(ICMOL), University of Valencia, c/Catedrático José Beltrán 2,
46980 Valencia, Paterna, Spain
3
Dipartimento di Chimica e Tecnologie Chimiche (CTC), Università
della Calabria, 87036 Rende, Cosenza, Italy
Microchimica Acta (2020) 187: 201
https://doi.org/10.1007/s00604-020-4185-z
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