MRS Communications

© The Author(s), under exclusive licence to The Materials Research Society, 2024
https://doi.org/10.1557/s43579-024-00683-9

Research Letter

An eco‑friendly and low‑cost method for obtaining bioMOFs

from glutamic acid
Élvio Antônio de Campos , Natália Cristina Zanotelli, Rodrigo Vieira Rodrigues, Ronan Faria Freire de Souza, Silv
ia Denofre de Campos, Sandro Fernando Stolf, Center of Engineering and Exact Sciences, Western Paraná State University (UNIOESTE), Toledo
Campus, 3141 Guaíra Street, Toledo, PR 85903‑220, Brazil
Address all correspondence to Élvio Antônio Campos at [email protected]

(Received 8 July 2024; accepted 25 November 2024)

Abstract
The combination of C ­ o2+, ­Cu2+, or Z­ n2+ with glutamate result in compounds [M(glutamate)(H2O)2]n that are classified as MBioFs (metal–biomolecule
frameworks). These can be prepared by different methods that result in orthorhombic crystals from space group P212121. We present the results
of simple reactions carried out in aqueous media without any pH controller through the reaction of the basic metal carbonates with glutamic acid.
Due to the fast precipitation part of the products is retained when filtering and this was recovered by treatment with a 1.5% (v/v) acetic acid solution
between 50 and 70°C, which constitutes a possible recrystallization.

Introduction out in aqueous conditions under heating, which result in iso-

The supramolecular arrangement of biomolecules with metal structural compounds. Additionally, the results of a purification
ions gives rise to a subclass of MOFs, namely biologically procedure of the obtained compounds are presented.
derived MOFs (bioMOFs), and it can be made of multifunc-
tional and commercially available biologically derived ligands
(bio-ligands) such as amino acids, peptides, nucleobases, and Material and methods
saccharides.[1] Considering amino acids as solely organic For the synthesis procedure, glutamic acid ­ ( H 2 Glu:
ligands forming bioMOFs, we can highlight those formed by ­ O2C(CH2)2CH(NH2)CO2H > 99%—CAS no. 56–86-0), cobalt
H
­aspartic[2] and ­glutamic[3–5] acids, cysteine,[6] and tyrosine.[7] (II) carbonate hydrate (­ CoCO3·xH2O 43–47% Co—CAS no.
The glutamic acid (­ H2Glu) stands out for forming com- 57454–67-8), basic copper (II) carbonate ­(CuCO3 · Cu(OH)2—
pounds with distinct applications such as drug carrier,[8] cata- CAS no. 12069-69-1), and basic zinc carbonate (­ 2ZnCO3 ·
lyst,[9] and enantiomer separation.[10] Among them, one can 3Zn(OH)2—CAS no. 5263-02-5) were used, all of them from
cite the compounds formed by glutamic acid with cobalt,[3] Sigma Aldrich.
copper, [4] and z­ inc [5] with the general formula [M(Glu)
(H2O)·H2O]n (where M = ­Co2+, ­Cu2+ or Z ­ n2+, and Glu is the Synthesis procedure
glutamate dianion). The procedure to prepare the compounds [M(Glu)(H2O)·H2O]n
These bioMOFs can be prepared by different methods, such is previously described.[16] Briefly, the [Co(Glu)(H2O)·H2O]n
as the slow aqueous solution evaporation in stoichiometric was prepared by suspension of 0.026 mol (4.02 g) of
mixtures of glutamic acid with metal salts or oxides, with or ­C oCO 3·xH 2O in 60 mL of water at 50°C and 0.02 mol
without the pH control.[4,5] Alternatively, it can be prepared by (2.9426 g) of glutamic acid were added in small portions. The
hydrothermal method using triethylamine as a proton captor.[11] mixture was kept under magnetic stirring until the release of
In both cases, orthorhombic crystals belonging to the P212121 ­CO2 stopped. The solution was then hot filtered and condi-
space group are obtained in variable yields. Although the struc- tioned to age for one week, after that the crystals formed were
tures of these BioMOFs with glutamic acid were solved fairly filtered off, washed with distilled water and ethanol, and dried
recently, they have been attracting attention for a long time, as at 60°C for 2 h.
in the works by S ­ arma[12] and Gramaccioli.[13,14] Compounds The [Cu(Glu)(H2O)·H2O)2]n was prepared by dissolution
of the same composition but with a different structure are of 0.02 mol (2.9426 g) of glutamic acid in 250 mL of pure
described by Can et al.,[15] for which they attest to different water at 90–95°C, and 0.01 mol (3.7618 g) of C ­ uCO3·Cu(OH)2
properties such as antibacterial agents, blood compatibility, were added in small portions under magnetic stirring. After
biocompatibility and sensors properties. the release of ­CO2 stopped, the solution was hot-filtered and
Herein we present the results of simple reactions of cobalt, aged for one week. The crystals were filtered off and washed
copper, and zinc basic carbonates with glutamic acid, carried similarly to the [Co(Glu)(H2O)·H2O]n.

Vol.:(0123456789)

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 To prepare the [Zn(Glu)(H2O)·H2O]n, 0.02 mol (2.9426 g) carbonates, because the increase in temperature contributed to
of glutamic acid in 250 mL of pure water at 90–95°C and the formation of cobalt oxides.
0.004 mol (2.1960 g) of ­2ZnCO3·3Zn(OH)2 were carefully
CoCO3 + H2 Glu + H2 O → [Co(Glu)(H2 O) · H2 O] + CO2
added in very small portions without any stirring, due to the
(1)
immediate formation of the [Zn(Glu)(H2O)·H2O]n. After the CuCO3 · Cu(OH)2 + H2 Glu + H2 O
addition was completed, the reaction mixture was left to stand (2)
→ [Cu(Glu)(H2 O) · H2 O] + Cu(OH)2 + CO2
for one week and, after that, the crystals were separated as
described for the other compounds.
2ZnCO3 · 3Zn(OH)2 + 5H2 Glu → 5[Zn(Glu)(H2 O) · H2 O] + 2CO2
(3)
Reprecipitation method
The reprecipitation method was applied to the solids formed in The reactions with copper (47% yield) and zinc (85% yield)
the reaction with cobalt carbonate and basic copper (II) carbon- basic carbonates occur under heating between 90 and 95°C.
ate that were retained during hot filtration, as well as to the zinc However, only the reaction with basic copper (II) carbonate
compound, like a recrystallization process. In the case of the requires stirring, whereas to obtain larger and well-formed
reactions with cobalt and copper carbonates, part of them can crystals, the reaction with basic zinc carbonate needs to be
be precipitated and retained with by-products of the respective carried out without any stirring, adding the carbonate to the
reactions due to the rapid formation of the products. The solids glutamic acid solution slowly and in small portions.
must be treated with an aqueous solution of acetic acid 1.5%
(v/v) to recover them. The required amount of this solution PXRD
depends on the amount of material retained on filtration, but for All of these reactions lead to the formation of crystalline com-
the quantities considered in this study, 100 mL are sufficient. pounds. The powder X-ray diffractograms [Figs. 1(A.II, B.II
The impure solid must be treated with the acetic acid solution at and C.II)] of such compounds showed that they have identi-
70°C under stirring. The solution should be hot-filtered, and the cal structures to those of compounds of the same metal–ligand
filtrate volume should be reduced to approximately 30% of the combination obtained by other methods and which are reg-
initial volume with gentle heating (maximum 70℃). After that, istered in the CCDC database under the numbers 188911
the solution should be left to stand for one week for crystal- ([Co(Glu)(H2O)·H2O]n), 1,255,390 ([Cu(Glu)(H2O)·H2O]n),
lization. Crystal formation is pH-dependent. If, after one week, and 1,501,246 ([Zn(Glu)(H2O)·H2O]n. They form orthorhom-
they still have not formed, a few drops (2 to 3) of a 10% (w/v) bic crystals belonging to the P212121 space group.
sodium carbonate solution should be added to start precipita- The metal:ligand ratio in these bioMOFs is 1:1. However,
tion. After crystallization, the solid must be filtered, washed since the ligand has two carboxylate groups and one -NH2
with water and ethanol, and dried for 2 h at 60°C. group, the arrangement, presented in Fig. 2, consists of three
amino acid residues bound to each metal ion. One of the amino
acid residues coordinates through an oxygen atom of the car-
Characterization boxylate and the –NH2, forming a 5-membered chelate, and
Powder X-ray diffraction (PXRD) data were obtained using a the other coordinates through the carboxylate group of the
Bruker diffractometer, model D2 6 Phaser, using Cu-Kα radia- amino acid side chain. The second oxygen atom of the car-
tion (λ = 1.5418 Å), 10 mA current and 30 kV voltage in the 2θ boxylate forming the 5-membered chelate of a neighbouring
range from 5° to 60° with a variation of 0.05° ­s−1. metal centre is the third amino acid residue bonded to a metal
The electronic spectra were obtained from bioMOFs solu- ion. A water molecule completes the hexacoordinated environ-
tion and the solids by photoacoustic spectroscopy. For the solu- ment of the metal ion, and a second water molecule remains
tions, ­10–4 mol of each compound were dissolved in 10 mL of hosted in the structure through hydrogen bonds with the car-
aqueous acetic acid solution 1.5% (v/v) and the spectra were boxyl oxygens.
obtained in a Lambda XLS Perkin Elmer UV–Vis spectropho- The overall reaction to the bioMOFs formation shows that
tometer. The photoacoustic spectra were collected in a home- the carbonate acts as a proton consumer, not requiring any addi-
made photoacoustic cell with a fused silica window using a tional pH controller, and releasing C ­ O2. However, in the case
Newport high pressure Xe 6269 source and a Cornerstone 130 of the synthesis of [Cu(Glu)(H2O)·H2O]n, unlike the synthesis
1/8 m CS130-USB-1-MC monochromator. of [Zn(Glu)(H2O)·H2O]n], the separation of Cu(OH)2 after the
cessation of C­ O2 release becomes necessary, since it remains
inert in presence of glutamic acid. The reasons Cu(OH)2 does
Results and Discussion not react with glutamic acid, whereas Zn(OH)2 does, have been
The reactions to obtain the bioMOfs (Eqs. 1–3) occurred under previously discussed.[16]
specific conditions for each metallic carbonate. For the reaction The powder diffractograms of the solids retained dur-
with ­CoCO3, the best yields (43% based on glutamic acid) were ing hot filtration, Figs. 1(A.III and B.III), show that they
obtained at lower temperatures than those used for the other are, respectively, the cobalt and copper bioMOFs with some

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 Research Letter

A
B

Figure 1.  PXRD of the bioMOFs (A) [Co(Glu)(H2O)·H2O]n: (I) calculated, (II) as obtained, (III) solid retained during hot filtration, and (IV)
solid obtained by reprecipitation. (B) [Cu(Glu)(H2O)·H2O]n: (I) calculated, (II) as obtained, (III) solid retained during hot filtration, and (IV)
solid obtained by reprecipitation. (C) [Zn(Glu)(H2O)·H2O]n (I) calculated, (II) obtained obtained in excess of glutamic acid (5% in mass), (III)
obtained in glutamic acid:zinc 1:1 stoichiometric conditions, and (IV) solid obtained by reprecipitation.

contaminants, as the characteristic peaks of the respective the final pH of the reaction medium’s solution is close to 7.
pure bioMOFs are broadened, and additional peaks are noted, The diffractogram of the final residue obtained after the re-
as well as some variations in the baseline. In the reaction to precipitation process indicates it is amorphous. In the reac-
obtain [Co(Glu)(H2O)·H2O]n, it is possible to form cobalt(II) tion to obtain [Cu(Glu)(H2O)·H2O]n, the solid retained in the
­dihydroxycarbonate[17] and oxidized cobalt species,[18] since re-precipitation is Cu(OH)2.

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 In some replicates of the preparation of [Zn(Glu)
(H2O)·H2O]n, the presence of broad and low-intensity peaks
at 2θ values near 13º and 24º [Fig. 1(C.III)] was observed in
the respective diffractogram. These peaks are not present in
the diffractogram of the compound obtained after re-precip-
itation [Fig. 1(C.IV)]. The presence of such peaks indicates
that the compound obtained primarily is contaminated with
the basic zinc carbonate remaining from the synthesis pro-
cess, since these peaks are present in the diffractogram of
­2ZnCO3·3Zn(OH)2 (Figure S1).
However, the diffractogram of the solids formed from the
filtrate, which was obtained by reprecipitation, Figs. 1(A.IV,
B.IV and C.IV), corresponds to the respective bioMOFs with
a reasonable degree of purity, given the similarity of such dif-
fractograms with the respective calculated diffractograms and
the diffractograms of Figs. 1(A.II, B.II and C.II).

Electronic spectra
Overall, although some differences were found, the results
obtained by conventional UV–Vis absorption spectroscopy
are equivalent to those obtained by photoacoustic (PA) spec-
Figure 2.  Hexacoordinated arrangement of the metal ions in troscopy.[19] The electronic spectra of the bioMOFs [Co(Glu)
bioMOFs [M(Glu)(H2O)· ­H2O]n (M = ­Co2+, ­Cu2+, and ­Zn2+)—Green: (H2O)·H2O]n and [Cu(Glu)(H2O)·H2O]n) in solution were
metal ion; Red: Oxygen; Light blue: nitrogen; Gray: carbon. The obtained by conventional absorption spectroscopy, whereas
hydrogen atoms were suppressed for better visualization. photoacoustic spectroscopy was used to obtain the spectra of
the bioMOFs (all three compounds) in the solid state.

A B

Figure 3.  The electronic spectra of [Co(Glu)(H2O)·H2O]n (A) dissolved in 1.5% (v/v) acetic acid aqueous solution ­(10–2 mol ­L−1) obtained by
conventional spectroscopy, and (B) the pure solid obtained by photoacoustic spectroscopy.

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 Research Letter

In the electronic spectrum of [Co(Glu)(H2O)·H2O]n in one observed in the spectrum of the same compound in solu-
solution, Fig. 3(A), a band centered at 513 nm and a shoul- tion (750 nm). The charge-transfer band is absent in PA spec-
der at approximately 468 nm were observed. They are due to tra due to the lack of solvent. Instead, a moderately narrow
the transitions 4T1g(F) → 4A2g and 4T1g(F) → 4T1g(P), respec- band of medium intensity is observed at 250 nm for [Co(Glu)
tively, from a high-spin d­ 7 system. The electronic spectrum of (H2O)·H2O]n, and 300 nm for [Cu(Glu)(H 2O)·H2O]n. This
[Cu(Glu)(H2O)·H2O]n in solution, Fig. 4(A), shows a broad band is probably caused by the transition between the valence
and asymmetric band with a maximum at 750 nm due to the band (VB) and the conduction band (CB) of the solids that
transition 2T2g → 2Eg. The asymmetry of this band is attributed behave as semiconductors. The energy gap value between
to the Jahn–Teller distortion. In the electronic spectra of two VB and CB estimated graphically (Figures S2) was 4.3 eV
compounds in solution, an intense absorption occurs below for [Co(Glu)(H2O)·H2O]n, 3.6 eV for[Cu(Glu)(H2O)·H2O]n
300 nm, probably due to a change transfer band promoted by and 3.9 eV for [Zn(Glu)(H2O)·H2O]n.
the interaction with the solvent. The photoacoustic spectra presented broader bands than
In the photoacoustic spectrum of [Co(Glu)(H2O)·H2O]n, the conventional absorption spectra from solutions. Never-
Fig. 3(B), a broad absorption band ranging between 630 and theless, the differences between the electronic spectra of the
390 nm can be observed, seemingly with multiple absorp- solids and the solutions indicate that, most likely, dissolv-
tion maxima. The presence of a higher number of bands in ing the bioMOFs in acetic acid solution destroys the supra-
the solid’s photoacoustic spectrum is likely the result of both molecular structure of the compounds, including changes in
the rigidity of the supramolecular structure and the distortion the metal coordination sphere. The dissolution of [Co(Glu)
of octahedral symmetry, unfolding the t­2g orbitals (octahedral (H2O)·H2O]n contributes to the shift of the bands to higher
system) into orbitals of symmetry a1’ and e’ (trigonal prismatic energy values, while the dissolution of [Cu(Glu)(H2O)·H2O]n
system).[20] In the PA spectrum of [Cu(Glu)(H2O)·H2O]n, the shifts to lower values. The spectra of the cobalt and copper
d-d transition band is less evident since the PA spectra were bioMOFs in solution resemble those observed for the ions
taken between 700 and 225 nm. [Co(H2O)6]2+[21] and [Cu(H2O)6]2+,[22] indicating that pos-
However, the absorption maximum for the 2T2g → 2Eg tran- sibly water molecules may have partially replaced carboxyl
sition occurs at approximately 670 nm, a value well below the groups coordinated to metal ions when dissolving bioMOFs.

A B

Figure 4.  The electronic spectra of [Cu(Glu)(H2O)·H2O]n (A) dissolved in 1.5% (v/v) acetic acid aqueous solution ­(10–2 mol ­L−1) obtained by
conventional spectroscopy, and (B) the pure solid obtained by photoacoustic spectroscopy.

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Author contributions org/​10.​1107/​S0365​110X6​60035​17
E. A de Campos, R. F. F. de Souza and S. D de Campos were 14. C.M. Gramaccioli, Acta Crystal. 21, 600 (1966). https://​doi.​org/​10.​1107/​
S0365​110X6​60035​29
involved in planning and supervised the work and wrote the 15. M. Can, S. Demirci, A.K. Sunol, N. Sahiner, Microporous Mesoporous
drafted the manuscript. N. C. Zanotelli and R. V. Rodrigues Mater. 309, 110533 (2020). https://​doi.​org/​10.​1016/j.​micro​meso.​2020.​
performed the measurements (except the photoacoustic meas- 110533
urements), processed the experimental data, and designed the 16. N.C. Zanotelli, R.V. Rodrigues, R.F.F. de Souza, S.D. de Campos, E.A. de
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figures. S. F. Stolf performed the photoacoustic analysis. All jchem​ed.​2c008​49
authors discussed the results on the manuscript. 17. Z.-H. Peng, F. He, H. Jia, X.-B. Li, Q.-S. Zhou, T.-G. Qi, G.-H. Liu, Trans.
Nonferrous Met. Soc. China 30, 509 (2020). https://​d oi.​o rg/​1 0.​1 016/​
S1003-​6326(20)​65231-1
Funding 18. J.B. Gerken, J.G. McAlpin, J.Y.C. Chen, M.L. Rigsby, W.H. Casey, R.D. Britt,
S.S. Stahl, J. Am. Chem. Soc. 133, 14431 (2011). https://​doi.​org/​10.​1021/​
This work did not involve funding.
ja205​647m
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Data availability 20. R. Hoffmann, J.M. Howell, A.R. Rossi, J. Am. Chem. Soc. 98, 2484 (1976).
The data will made available if requested. https://​doi.​org/​10.​1021/​ja004​25a016
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Declarations 10.​1016/​0584-​8539(70)​80074-5
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