ArticlePublisher preview available

Bio-metal-organic frameworks for molecular recognition and sorbent extraction of hydrophilic vitamins followed by their determination using HPLC-UV

Authors:
To read the full-text of this research, you can request a copy directly from the authors.

Abstract and Figures

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 juices and 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. A bio-MOF as SPE sorbent was prepared and applied to the extraction of B-vitamins in fruit juices and energy drinks.
This content is subject to copyright. Terms and conditions apply.
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 [79]. 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), Universi
della Calabria, 87036 Rende, Cosenza, Italy
Microchimica Acta (2020) 187: 201
https://doi.org/10.1007/s00604-020-4185-z
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
... Moreover, Pé rez-Cejuela group prepared a bio-MOF, including hexagonal frameworks modified with L-serine in a bulk form. The bio-MOF contains a lot of hydroxyl groups that can connect directly to other supramolecular, recognizing B-vitamins extraction [77]. ...
Article
Metal-organic framework (MOF) materials provide unprecedented opportunities for evaluating valuable compounds for various medical applications. MOFs merged with biomolecules, used as novel biomaterials, have become particularly useful in biological environments. Bio-MOFs can be promising materials in the global to avoid utilization above toxicological substances. Bio-MOFs with crystallin and porosity nature offer flexible structure via bio-linker and metal node variation, which improves their wide applicability in medical science.
... MOFs are coordination polymers prepared from metal ions (clusters) and organic linkers, giving rise to extended 3-D open framework structures, with incorporated solvent molecules [18]. MOFs have rapidly found their way in many applications such as separations, gas storage, heterogenous catalyses, molecular recognition, and drug delivery [19][20][21][22][23]. Different metals such as Al, Ni, Co, Cu, Zn, Cr, Ga, Fe, V, and Zr have been used to construct MOFs [24][25][26]. ...
Article
Full-text available
The vast use of polyethylene terephthalate (PET) drinking water bottles has increased dramatically worldwide in recent decades, inflicting severe consequences on the environment. According to the latest survey, a million plastic bottles are bought around the globe every minute. The non-biodegradable nature of PET materials has led to a huge accumulation of plastic in waste landfills. Among the current recycling methods used to solve this environmental problem is chemical recycling. In this method, PET bottles are converted back cleanly into their starting materials: terephthalic acid and ethylene glycol. This paper unveils the exploitation of recycling products from PET bottles and aluminium scraps in order to prepare a metal-organic framework (MOF) material. The characterization of the prepared MOF substance was carried out using different techniques such as IR, XRD, SEM and elemental analysis.
... In 2020, a bio-MOF obtained from L-serine amino acid was synthesized in bulk form and investigated as an absorbent for the B-vitamins extraction in juices and the molecular recognition, followed using HPLC-UV assay [185]. The bio-MOF showed the excellent extraction performance of SPE in B-vitamins with low LODs, acceptable reusability, and high extraction recovery. ...
Article
Metal-organic frameworks (MOFs), known as highly ordered crystalline hybrid structures, are the products of coordination polymerization of transition metals and organic ligands. MOFs are best known for their extensive specific surface area, hierarchically porous and tailorable 1D, 2D, or 3D micro-and nanostructure, and acceptable biocompatibility. Because of the multiplicity of metallic and organic units used in MOFs synthesis, it is possible to serve chemistry as the determining factor for designing precise MOFs as building blocks of advanced biological materials and systems. Recently, green MOF synthesis has received much more attention for nanobiomedicine usage. Herein, we review green solvents, ligands, linkers, auxiliary linkers, and sustainable organic precursors used to synthesize green MOFs. First, MOFs were classified in terms of their general toxicity level and biological behavior by considering the chemistry of ligands, linkers, and green organic precursors. Second, applications of bio-MOFs and nano-MOFs in medicine were categorized. Third, usage of green MOFs as pro-drug and their potential and effects related to bioimaging, drug delivery, and multimodal therapeutics were systematically reviewed and discussed based on chemistry. Fourth, concluding remarks and challenging aspects of future developments of bio-MOFs and nano-MOFs were underlined.
... The election of this family of MOFs is not accidental. This is based on their good mechanical properties, which have already permitted their processability as pellets 29 or mixed matrix membranes 51 (MMM-MOFs), their proven air and water stability 53 (neutral and basic media), and their excellent performances in the removal of both inorganic 29,51 (Hg 2+ ) and organic contaminants (dyes 54 or vitamins 49,55 ), recently reported for 1-4, in the presence of other metal cations and inorganic anions usually present in potable drinking water. 29,30,35,54 The main reasons that lie at the origin of such remarkable capture properties are two-fold: (i) These MOFs feature channels decorated with different functional groups, which can be tuned depending on the nature of the chosen amino acid residue (-CH2OH, -CH(CH3)OH, -CH2SCH3 and/or -CH2CH2SCH3), and (ii) these amino acid residues exhibit a high degree of adaptability, 56 being capable to accommodate and adjust to guest molecules by maximizing hostguest interactions with the contaminant. ...
Article
Stereoselective chiral molecules are responsible for specific biological functions in nature. At present, more than half of the prescribed drugs are chiral. Living organisms display divergent pharmacological responses to the enantiomers, leading to altered toxicity, pharmacokinetics, and pharmacodynamics. Thus, chiral analysis, separation, and extraction are crucial for ensuring enantiomeric purity to develop safe and effective medication. In recent times, metal–organic frameworks (MOFs) with appealing structures are gaining importance because of their fascinating properties as a sorbent and stationary phase. MOFs are crystalline porous solid materials built by interconnecting metal ions or clusters and organic linkers. This review explores the advancements in MOFs for the isolation and separation of chiral active pharmaceutical drugs.
Article
Full-text available
The search for efficient technologies empowering the selective capture of environmentally harmful heavy metals from wastewater treatment plants, at affordable prices, attracts wide interest but constitutes an important technological challenge. We report here an eco-friendly single-walled carbon nanotube buckypaper (SWCNT-BP) enriched with a multivariate amino acid-based metal–organic framework (MTV-MOF) for the efficient and selective removal of Pb2+ in multicomponent water systems. Pristine MTV-MOF was easily immobilized within the porous network of entangled SWCNTs, thus obtaining a stable self-standing adsorbing membrane filter (MTV-MOF/SWCNT-BP). SWCNT-BP alone shows a moderately good removal performance with a maximum adsorption capacity of 180 mg·g–1 and a considerable selectivity for Pb(II) ions in highly concentrated multi-ion solutions over a wide range of lead concentration (from 200 to 10000 ppb). Remarkably, these features were outperformed with the hybrid membrane filter MTV-MOF/SWCNT-BP, exhibiting enhanced selectivity and adsorption capacity (310 mg·g–1, which is up to 42% higher than that of the neat SWCNT-BP) and consequently enabling a more efficient and selective removal of Pb2+ from aqueous media. MTV-MOF/SWCNT-BP was able to reduce [Pb2+] from the dangerous 1000 ppb level to acceptable limits for drinking water, below 10 ppb, as established by the current EPA and WHO limits. Thus, the eco-friendly composite MTV-MOF/SWCNT-BP shows the potential to be effectively used several times as a reliable adsorbent for Pb2+ removal for household drinking water or in industrial treatment plants for water and wastewater lead decontamination.
Chapter
Reticular materials form through strong bonding of various building blocks, leading to the formation of highly porous crystalline structures. Given the diversity of the available building units and the easily modification and functionalization of these materials, a huge variety of reticular materials can be obtained, which can be classified as metal–organic (MOFs) or covalent-organic (COFs) frameworks, depending on the nature of the building blocks. Apart from their impressive surface area and synthetic versatility, they also present adequate physicochemical and thermal stability, and can be easily synthesized together with other materials to prepare composites with attractive characteristics. All these properties make them potential candidates to prepare novel sorbents for analytical sample preparation strategies. This chapter summarizes the incorporation of MOFs, COFs, and their composites in different sorbent-based extraction methods, paying special attention to the evolution and recent advances in the field, together with their preparation and most relevant analytical applications.
Chapter
Ionic liquids (ILs) emerged as a greener alternative to conventional organic solvents thanks to their low volatility and flammability and their wide liquid-state window. These solvents have demonstrated special features that have found a broad application in analytical sample preparation. In particular, ILs are tunable and can be adapted to extract a given analyte by the proper selection of their constituent ions. This chapter provides a general overview of the potential of ILs in the (micro)extraction context, starting from the description of neat or conventional ILs, which allows explaining the main properties and benefits of these solvents. The chapter will also cover other relevant ILs-based materials like magnetic ionic liquids (MILs) and polymeric ILs (PILs). The content of this chapter is intentionally asymmetrical to give a current picture of the field since not all the materials are equally developed. For example, conventional ILs have a larger story, and therefore the main milestones and general applications are mentioned. On the contrary, more specific information about MILs and PILs is presented.
Article
Edible ligand-metal-organic frameworks (EL-MOFs) have a tremendous potential in practical applications including but not limiting to biomedicine, chemistry, environment, food, and pharmacy. EL-MOFs not only retain advantages of conventional MOFs with high porosity, large specific surface area, flexible pore structure, and abundant binding sites, but also bring desirable appeals like nontoxicity, biocompatibility, and environmental friendliness. Here, the synthesis and structures of EL-MOFs were firstly introduced. Secondly, their physical and chemical properties including thermal stability, chemical stability, and adsorption and desorption were objectively evaluated. Thirdly, biocompatibility and potential applications of EL-MOFs, especially reported in the last five years, were comprehensively summarized and discussed. At last, potential opportunities and challenges of EL-MOFs were prospected.
Article
Cyclodextrins (CDs) are a unique class of molecules that are naturally available via degradation of starchy molecules. Their toroidal structure and abundant presence of hydroxyl groups have given scientists exceptional leverage resulting in synthesizing novel molecules for applications ranging from food packaging, controlled release of small molecules, antibacterial coating, agriculture, and air and water filtration. With the advent of nanotechnology, CDs have positioned itself in variety of forms such as their ability to act as capping/reducing agent for metallic nanoparticles, or form stable nanofibers or nanoparticles or nano micelles, which can be subsequently utilized for sophisticated applications. In this review we summarize researches on the presence of CDs in various aspects of nanotechnology ranging from nanoparticles, nanorods, nanomicelles, and nanofibers. In addition, through this review we provide state-of-the-art applications that are being carried out using these nanostructures.
Article
Full-text available
Metal organic frameworks (MOFs) are considered as a group of compounds, either metal ions or clusters, harmonized with organic ligands to form one or some dimensional structures. In addition to resilient bonds between inorganic and organic units, reticular synthesis creates MOFs, accurate selection of constituents of which can produce high thermal and chemical stability and crystals of ultrahigh porosity. Other solids have not shown the same accuracy normally used in chemical modification and even the capability of increasing their metrics with no modification of the underlying topology. With shape of building units and chemical compositions multiplying based on specific structures, MOFs might result in compounds that propose a synergistic mixture of features. This study presents up to date advances in both synthesis methods of MOFs and structural characteristics. Furthermore, the use of MOFs in different fields such as the removal of absorption and separation of toxic substances from gas and liquid, catalysts, a variety of sensors, storage of clean energies and environmental applications, medical and biological applications, and optoelectronic equipment is included.
Article
Full-text available
Metal–organic frameworks (MOFs) are porous crystalline materials with large surface areas, uniform pore size, and tunable selectivity. In the last few years, the number of analytical applications of MOFs has been growing constantly. However, the direct use of as-synthesized MOFs in packed column format is rather limited for analytical separations because of the small size and non-spherical shape of MOF crystals. In this review, we outline and critically discuss the advantages and limitations of the different methods described to immobilize MOFs into functional supports for analytical separations, including beads, monoliths, and fibers. These methods are based on embedding MOF crystals into functional supports, in situ MOF growth, controlled layer-by-layer MOF growth, or the in situ conversion of immobilized MOF metal oxide precursors. Representative examples of immobilized MOFs for sample preparation and chromatographic separation are overviewed. We also overview recent progress on the use of MOFs as precursors to obtain other functional materials such as layered double hydroxides or porous carbons.
Article
Full-text available
This review (with 85 refs.) summarizes the recent literature on the adsorption of common aromatic pollutants by using modified metal-organic frameworks (MOFs). Four kinds of aromatic pollutants are discussed, namely benzene homologues, polycyclic aromatic hydrocarbons (PAHs), organic dyes and their intermediates, and pharmaceuticals and personal care products (PPCPs). MOFs are shown to be excellent adsorbents that can be employed to both the elimination of pollutants and to their extraction and quantitation. Adsorption mechanisms and interactions between aromatic pollutants and MOFs are discussed. Finally, the actual challenges of existence and the perspective routes towards future improvements in the field are addressed. Graphical abstractRecent advance on adsorption of common aromatic pollutants including benzene series, polycyclic aromatic hydrocarbons, organic dyes and their intermediates, pharmaceuticals and personal care products by metal-organic frameworks.
Article
Full-text available
A new labeling reagent for vitamin analysis, 2-amino-10-ethyl acridine ketone (AEAO), has been synthesized and successfully applied to the analysis of vitamin B3 and vitamin B7 in different tea samples. The reaction of AEAO with vitamins could proceed easily and quickly in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC) as condensing reagent within 45 min. The derivatives exhibited excellent fluorescence property with excitation and emission wavelengths of 290 nm and 430 nm, respectively. Response surface methodology (RSM) was applied to the optimization of pre-column derivatization. Solid phase extraction with HLB cartridges was used for the extraction and purification of water-soluble vitamins in tea samples. The LODs for vitamin B3 and vitamin B7 were 2.56 and 2.22 ng mL⁻¹, respectively. The proposed method was successfully applied to the analysis of vitamin B3 and vitamin B7 in different tea samples. The study provided a highly sensitive method for accurate analysis of trace vitamins from natural products.
Article
Full-text available
Separation is an important industrial step with critical roles in the chemical, petrochemical, pharmaceutical, and nuclear industries, as well as in many other fields. Although much progress has been made, the development of better separation technologies, especially through the discovery of high‐performance separation materials, continues to attract increasing interest due to concerns over factors such as efficiency, health and environmental impacts, and the cost of existing methods. Metal–organic frameworks (MOFs), a rapidly expanding family of crystalline porous materials, have shown great promise to address various separation challenges due to their well‐defined pore size and unprecedented tunability in both composition and pore geometry. In the past decade, extensive research is performed on applications of MOF materials, including separation and capture of many gases and vapors, and liquid‐phase separation involving both liquid mixtures and solutions. MOFs also bring new opportunities in enantioselective separation and are amenable to morphological control such as fabrication of membranes for enhanced separation outcomes. Here, some of the latest progress in the applications of MOFs for several key separation issues, with emphasis on newly synthesized MOF materials and the impact of their compositional and structural features on separation properties, are reviewed and highlighted.
Article
Full-text available
Gas storage and separation are closely associated with the alleviation of greenhouse effect, the widespread use of clean energy, the control of toxic gases, and various other aspects in human society. In this review, we highlight the recent advances in gas storage and separation using metal-organic frameworks (MOFs). In addition to summarizing the gas uptakes of some benchmark MOFs, we emphasize on the desired chemical properties of MOFs for different gas storage/separation scenarios. Greenhouse gases (CO2), energy-related gases (H2 and CH4), and toxic gases (CO and NH3) are covered in the review.
Article
In this review, recent advances in the analysis of water-soluble vitamins (WSVs) have been reported considering the advantages and disadvantages of various extraction, separation and detection techniques, commonly used for their quantification. Acid hydrolysis, enzyme treatment, SPE based methods and some other extraction methods have been discussed. Particular attention has been devoted to the analytical techniques based on liquid chromatography and electrophoresis. Furthermore, suitability and selectivity of hydrophilic interaction liquid chromatography (HILIC) for WSVs has been discussed in detail. Problems related to these techniques and their possible solutions have also been considered. Special focus has been given to the applications of liquid chromatography (since 2014-2019) for the simultaneous analysis of WSVs and their homologous in complex food samples.
Article
We report a novel metal-organic framework (MOF) featuring functional pores decorated with hydroxyl groups derived from the natural amino acid L-serine, which is able to establish specific interactions of different nature, strength and directionality with organic molecules of technological interest, i.e. ascorbic acid, pyridoxine, bupropion and 17-beta-estradiol, based on its different size and chemical nature. The ability of 1 to distinctly organize guest molecules within its channels, through the concomitant effect of different directing supramolecular host-guest interactions, enable to have unique insights, by means of single-crystal X-ray crystallography, on the host-guest interactions. These results increase our understanding on molecular recognition processes at MOFs, opening a myriad of potential technological applications in the near future.
Article
A novel green synthesis strategy was proposed for preparation of multi-template molecularly imprinted biopolymers (mt-MIBP) in aqueous media with less consumption of organic solvents, which were subsequently used as sorbents of ultrasound-assisted dispersive solid-phase extraction (d-SPE) for simultaneous recognition and efficient separation of B-family vitamins in juice samples followed by high performance liquid chromatography (HPLC) determination. The obtained mt-MIBP was fully characterized by SEM, FT-IR, TEM and BET. It offered high binding capacity, good selectivity and fast dynamics toward all the templates. Involved parameters in the d-SPE efficiency such as mt-MIBP mass, sonication time, and eluting/washing solvents’ types and volumes were concurrently investigated by central composite design (CCD) with rapidity and reliability. Under the optimum conditions, the developed mt-MIBP-d-SPE-HPLC method exhibited wide linear range, low limits of detection (LODs) and quantification (LOQs) within 1.2–5.5 µg L−1 and 4.0–18.4 µg L−1, respectively, and appropriate repeatability (relative standard deviation values (RSDs) below 4.2%, n=4). The high selectivity of this method makes it suitable for successful monitoring of vitamins in juice samples with satisfactory recoveries of 75.8–92.7%, 83.3–92.5% and 84.7–93.8% for vitamins riboflavin (B2), nicotinamide (B3) and pyridoxine (B6), respectively. The present study implied highly promising perspectives of water-compatible eco-friendly mt-MIBP for highly effective multi-residue analysis in complicated matrices.
Article
Biological metal-organic frameworks (BioMOFs) are a new class of crystalline porous materials developed in the last decade that represent a subclass of metal-organic frameworks (MOFs). Biomolecules introduced as components of MOFs confer biological compatibility for this emerging type of material, thus providing new opportunities for applications in biology, medicine, and a variety of other fields. In this review, to focus on host-guest chemistry and applications in biology and biochemistry, we provide an overview of recent examples of BioMOFs comprising multifunctional biomolecular ligands and transition metal ions. The bio-ligands include nucleobases, amino acids, polypeptides, proteins, cyclodextrin, porphyrin/metalloporphyrin and others. The host-guest chemistry of BioMOFs is highlighted in light of supramolecular recognition by different technologies. The potential applications of BioMOFs in several promising research fields such as drug delivery, enantioseparation and biomimetic catalysis are also summarized. In the last section, the outlook and possible challenges in advancing these research topics are illustrated.