The interaction of morin and morin-5’-sulfonic acid with lead(II): Study of the 1:1 complex formation process in aqueous solution

Maxim A. Lutoshkin 1 , Boris N. Kuznetsov 2 , 3 ,  and Vladimir A. Levdanskiy 2
  • 1 Université de Lyon, Université Claude Bernard Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et l’environnement de Lyon, Villeurbanne, France
  • 2 Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Science Center SB RAS”, Krasnoyarsk, Russian Federation
  • 3 Institute of Non-Ferrous Metals and Materials Science, Siberian Federal University, Krasnoyarsk, Russian Federation
Maxim A. Lutoshkin
  • Corresponding author
  • Université de Lyon, Université Claude Bernard Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et l’environnement de Lyon, Villeurbanne, France
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, Boris N. Kuznetsov
  • Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Science Center SB RAS”, Krasnoyarsk, Russian Federation
  • Institute of Non-Ferrous Metals and Materials Science, Siberian Federal University, Krasnoyarsk, Russian Federation
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and Vladimir A. Levdanskiy
  • Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Science Center SB RAS”, Krasnoyarsk, Russian Federation
  • Search for other articles:
  • degruyter.comGoogle Scholar

Abstract

This article focuses on the aqueous complexation between two flavonoids (morin and morinsulfonate) and Pb2+ at constant ionic strength I=0.5 M (NaClO4). The determination of stability constants of ML complexes were performed at wide pH range. Two obtained constants are 14.8 ± 0.1 and 15.2 ± 0.1 logarithmic units for morin and morin-5’-sulfonic acid, respectively. For estimating the thermodynamic stability of the complexes studied, the Def2-SV(P)/DFT/PBE0/SMD method has been used. Different computational models were tested to describe the data obtained. The theoretical values of logK reproduce the experimental parameters within reasonable errors.

1 Introduction

Morin and other flavonoids are a group of natural polyphenolic chemicals, widely distributed in the world of plants. These compounds have a variety of biological properties (Panche et al., 2016). Antioxidant (Pietta et al., 2000), anticancer (Batra and Sharma, 2013) and antibacterial (Cushnie and Lamb, 2005) activities are among the most essential characteristics of natural flavonoids. The presence of all these features results in wide applications of flavonoids and their derivatives in medicine and pharmacology.

Due to the availability of several -OH groups, all flavonoids including morin exhibit effective chelating capacity in solution. The various metal complexes of flavonoids described in the literature (Kasprzak et al., 2015; Samsonowicz and Regulska, 2017) were synthesized in aqueous media. Many of them are bioactive (de Souza and De Giovani, 2013; Stalin et al., 2014). Nevertheless, today not much is known about the chemistry of metal-morin complexes in solution. The biggest challenge to research is a low solubility of flavonoids in H2O. The poor water-solubility makes electronic absorption spectroscopy the only method that could truly reflect a condition of morin in solution. Also, the study of bonding abilities of morin and its derivative (morin-5’-sulfonic acid or morin sulfonate) with heavy metals can help to find the new application areas for these flavonoids.

The goal of this work was to investigate the interaction of morin and morin-5’-sulfonic acid (MSA) with Pb2+ in aqueous solution and interpreting these data using quantum-chemical simulation.

2 Results and discussion

2.1 UV-Vis study

The appearance of a new absorption peak at 370-460 nm in morin/MSA spectra (Figure 1) indicate about bonding with Pb2+. All measurements were carried out under an excess of lead(II) ions. The concentration of the ligands was constant in each series. All spectroscopic data are given in the supporting information (Tables S1 and S2).

Figure 1
Figure 1

The UV–Vis spectra and absorbance at single wavelength (404 nm) for Pb2+-Morin system; C(Morin) = 6.87·10-5 M; pH=2.80, I=0.5 M.

Citation: Main Group Metal Chemistry 42, 1; 10.1515/mgmc-2019-0007

ΔAmax is located near 405 nm for both systems (Figures S1 and S2). All equilibrium parameters were calculated at 404 and 406 nm for morin and MSA, respectively. As can be seen, the value of ΔA depends only on the metal concentration and the position of ΔAmax remains invariant for all series. In an earlier work (Bujonek et al., 1996), the domination of mono complex form of Pb2+-MSA has been shown. These facts attest to the formation only one complex as it is shown in Eq. 1.

PbH2Om2++HiL0PbH2O2Hi-nL2n++nH++m2H2O

The glycine-HCl buffer was used in the 2.20-3.40 pH interval. At pH below 2.2, the interaction morin/MSA-Pb2+ was too weak to be studied. Under these conditions, lead(II) cation can form complexes with glycine and OH. Along with this, the dissociation of a ligand must be taken into account. The following equations were used for the calculation of the “true”(K) stability constant (Petrov et al., 2015):

K=αMαLK
αM=1+βn[L]n
αL=1+KH[H+]

where K’ – conditional constant, KH is 1/Ka of ligands (Kopacz, 2003), is the stability constant of Pb2+-glycine (Casale et al., 1995) and Pb(OH)+ (Cruywagen and van de Water, 1993) complexes. Table 1 contains all the equilibrium parameters obtained. From these data the linear correlation between the conditional stability constants and pH is quite apparent. Figure 2 demonstrates this relationship. For both lines the inclination is approximately ≈ 1. This indicates bond breaking with one proton in course of the complexation process and formation PbL+ species (n=1 in Eq. 1).

Figure 2
Figure 2

The pH-logK’ relationship for Pb2+-MSA (1) and Pb2+-morin (2) systems.

Citation: Main Group Metal Chemistry 42, 1; 10.1515/mgmc-2019-0007

Table 1

The conditional (K’), true (K) stability constants, and extinctions (ε) for morin-Pb2+ and MSA-Pb2+ systems.

LigandpH ±K’logK’ ±logε ±logK ±
0.01*0.020.03**0.1
Morin3.401423 ± 963.154.1514.7
3.201044 ± 483.024.1514.8
3.00745 ± 342.874.1414.8
2.80496 ± 232.704.1314.9
2.60275 ± 122.444.1214.8
2.40182.5 ± 8.42.264.1014.8
MSA3.202870 ± 1333.463.8015.2
3.001673 ± 763.223.73
2.801125 ± 513.053.72
2.60640 ± 302.813.77
2.40449 ± 202.653.75
2.20248 ± 112.393.72

*The “±” values represent confidence limits (P = 0.95) throughout the article.

**The values are given for 404 (morin) and 406 (MSA) nm.

Under the same conditions, logK’ is higher for MSA but the “true” stability constant is almost equal for both flavonoids. A comparison of metal complexes of morin (Malesev and Kuntic, 2007) with Cu2+(logK=4.94), Zn2+ (logK=6.74), Ba2+(logK=4.55) and Pb2+ shows that the latter is one of the most stable coordination compound for this ligand. In addition, from all 1:1 metal-flavonoid complexes existing in aqueous media, Pb2+-morin is the most stable. In fact, only Fe3+-rutin (logK=44.1; Kasprzak et al., 2015) complex has a higher stability than the lead complex.

2.2 The DFT calculations

All possible tautomers of the complexes studied are collected in Scheme 1. Three chelates and two linear structures were chosen for computational procedures. The DFT calculations at level Def2-SV(P)/PBE0/SMD were carried out to assess the thermodynamic stability of each tautomer.

The absolute and relative calculated energies are presented in Table 2. The typical coordination number for lead(II) with O-donor ligands is 4 (Parr, 1997). Morin and MSA, being bidentate ligands, replace two molecules of water in the lead aqua complex upon complexation. In this regard, the assessment of dominated forms has been compiled for [Pb(H2O)2L]+ (L= morin or MSA) species.

Scheme 1
Scheme 1

The keto-enol equilibria for Pb2+-morin (R=H) and Pb2+-MSA (R=HSO3).

Citation: Main Group Metal Chemistry 42, 1; 10.1515/mgmc-2019-0007

Table 2

The absolute (a.u.) and relative (kJ·mol-1) energies for Pb2+- morin/MSA tautomers.

TautomerMorinMSA
absolute energyrelative energyabsolute energyrelative energy
N1-1446.92982141.87-2070.06250481.34
N2-1446.93731122.20-2070.07716642.85
N3-1446.9457680-2070.0934860
N4-1446.93149237.48-2070.08063733.73
N5-1446.92849745.35-2070.06429176.65

The calculations show the greater stability of N3 (coordination via 3-hydroxyl and 4-carbonyl groups) isomer for both systems. The optimized geometries for these tautomers are illustrated in Figure 3. A similar chelating site was proposed for the solid state 1:2 Pb-MSA complex in previous work (Kuzniar et al., 2008).

Figure 3
Figure 3

The optimization geometry for morin-Pb (B) and MSA-Pb (A).

Citation: Main Group Metal Chemistry 42, 1; 10.1515/mgmc-2019-0007

Aiming to verification of the results obtained and in search for an optimal computational protocol for describing of Morin/MSA-Pb2+ systems, the theoretical values of logK were calculated. Scheme 2 shows the thermodynamic cycle used for this goal. According to (Wander and Clark, 2008) the various forms Pb(H2O)m2+ (m=1-9) can be applicable for DFT simulations in water. In this work models with m =1, 2, 4, and 6 were tested. The results of the calculations are summarized in Table 3.

Scheme 2
Scheme 2

Thermodynamic cycle for the calculation of logKcalc.

Citation: Main Group Metal Chemistry 42, 1; 10.1515/mgmc-2019-0007

Table 3

The results of quantum-chemical estimation.

LigandmΔGsolv.+ ΔGgas,

kJ⋅mol-1
ΔEZPE,

kJ⋅mol-1
logKcalclogKexp
Morin1-144.14-24.0829.8914.8
2-39.49-35.5713.51
4124.63-49.92-12.37
6219.07-79.83-22.95
MSA1-72.90-7.3814.4215.2
232.11-20.87-1.97
4196.23-33.22-27.84
6290.67-63.14-38.42

As we can see, the optimal number of water molecules in the lead(II) aqua complex are 1 and 2 for MSA and morin, respectively. On closer scrutiny, one will also find that the sum of ΔGsolv. + ΔGgas is the main contributor in ΔΔGsolv. of the reaction. This could indicate the domination of solvent effect against covalent interaction in Pb2+- flavonoid complexes.

3 Conclusions

The complexation processes of morin and MSA with Pb2+ have been studied spectrophotometrically in aqueous solution. Twelve conditional and two “true” equilibrium stability constants were obtained in diapason pH 2.2-3.4 at I=0.5 M (NaClO4). The received logK (14.8 for morin and 15.2 for MSA) demonstrates the great stability of flavonoids-Pb2+ complexes. For the study of ketoenol equilibriums, the DFT computations have been implemented. The tautomer with coordination via 3-hydroxyl and 4-carbonyl groups was chosen as the most stable isomer for both complexes. Several computational protocols were tested for verification of the results obtained. It was established that using a small number of explicit water (1-2 molecules) makes it possible to achieve discrepancies of stability constants within ±1.0 logarithmic units.

Experimental

Materials and instrumentation

All chemicals were of analytical grade and used as supplied: HClO4, H2SO4, glycine, Pb(NO3)2, Morin (Sigma-Aldrich, ≥98%), NaClO4. The region of nitrate ion absorption (295-310 nm) does not overlap with the region (390-430 nm) studied. All stock solutions were obtained by dissolution of dry salts and ligand weights. The metal salts and ligands were dissolved in distilled water. The morin was diluted in selected sample from water-ethanol solution (50:50 vol.). The concentration of ethanol did not exceed 2% in the final solution. Morin-5-sulfonic acid was synthesized as reported in the literature (Kopacz, 2003). Its purity was tested by paper chromatography. The initial morin is not found in the final sample. Buffer solutions within the pH range from 2.20 to 3.60 were prepared with glycine-HClO4 buffer. The concentration of glycine in all solutions was constant and equal 0.05 M. The accurate desired pH values were obtained by adjusting the molarities of the buffer components in suitable amounts (Eliseeva and Bünzli, 2011). The ionic strength was maintained with NaClO4.

UV–Vis measurements

Conditional stability constants (K’) for monocomplex species were calculated from the Eq. 5-6 (Grebenyuk et al., 2002):

Acalcλ=εLλ(CL[ML])+εMλ(CM[ML])+εMLλ[ML]
[ML]=12[(1K+CL+CM)(1K+CL+CM)24CLCM]

where Aλcalc is an absorbance at a given wavelength and CM and CL were analytical concentrations of Pb2+ and ligand, respectively. The ελ is a value of molar extinction coefficient at single wavelength. The optimal values for K’ and ελ were found from the least squares analysis (Leggett, 1985):

f(CM,CL,K,εi)=i=1n(AiλAicalc)2K,εimin

Calculations of all equilibrium constants and molar extinction coefficients were performed using Wolfram Mathematica software package (https://www.wolfram.com/mathematica/)

DFT calculations

Ab initio calculations were carried out using the GAMESS US program package (Schmidt et al., 1993) on the cluster MVS-1000 M of the Institute of computational modeling SB RAS. The Def2-SV(P) (Weigend and Ahlrichs, 2005) basis set (including ECP pseudopotential for Pb) with the hybrid functional PBE0 (Adamo and Barone, 1999) under Grimme’s empirical correction (Grimme at al., 2010) was used for assessment. The solvent effects were evaluated using the SMD solvation model (Marenich et al., 2009). Geometry optimization was performed by density functional theory (DFT). The stability constants have been calculated using the Eq. 8-10 (Bryantsev et al., 2008):

logK=ΔΔGsolv./(2.303RT)
ΔΔGsolv.=ΔGgas+ΔGsolv.+ΔEzpe+Ecorr

where,

Ecorr.=-RTln([H2O])

Here, RTln([H2O]) is a free energy change associated with moving a solvent from a standard-state solution phase concentration of 1 M to a standard state of the pure liquid, 55.34 M (Vukovic et al., 2015). Ezpe is the value of zero point energy calculated from the frequency analysis. Values of Ggas(H+) and ΔGsolv.(H+) (-26.28 and -1108.27 kJ·mol-1, respectively) have been taken from the previous research (Lutoshkin and Kazachenko, 2017).

Acknowledgements

The authors would like to thank Dr. Franck Rataboul and Dr. Laurent Djakovitch for help with chemicals. Numerical computations were performed on the cluster MVS-1000 M of the Institute of computational modeling SB RAS.

References

  • Adamo C., Barone V., Toward reliable density functional methods without adjustable parameters: The PBE0 model. J. Chem. Phys., 1999, 110, 6158-6170.

    • Crossref
    • Export Citation
  • Batra P., Sharma A.K., Anti-cancer potential of flavonoids: recent trends and future perspectives. 3 Biotech., 2013, 3, 439-459.

    • PubMed
    • Export Citation
  • Bryantsev V.S., Mamadou S.D., Goddard III W.A., Calculation of solvation free energies of charged solutes using mixed cluster/ continuum models. J. Phys. Chem. B., 2008, 112, 9709-9719.

    • Crossref
    • PubMed
    • Export Citation
  • Bujonek B., Kopacz M., Novak D., Lead(II) and cadmium(II) complexes with quercetin-5′-sulfonic acid and sodium morin-5′-sulfonate. Russ. J. Gen. Chem., 1996, 66, 1037-1039.

  • Casale A., De Robertis A., De Stefano C., Gianguzza A., Patan G., Rigano C., et al., Thermodynamic parameters for the formation of glycine complexes with magnesium(II), calcium(II), lead(II), manganese(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) at different temperatures and ionic strengths, with particular reference to natural fluid conditions. Thermochim. Acta, 1995, 255, 109-141.

  • Cruywagen J.J., van de Water R.F., The hydrolysis of lead(II). A potentiometric and enthalpimetric study. Talanta, 1993, 40, 1091-1095.

    • Crossref
    • Export Citation
  • Cushnie T.P., Lamb A.J., Antimicrobial activity of flavonoids. Int. J. Antimicrob. Ag., 2005, 26, 343-356.

    • Crossref
    • Export Citation
  • Eliseeva S.V., Bünzli J.-C.G., Rare earths: jewels for functional materials of the future. New J. Chem., 2011, 35, 1165.

    • Crossref
    • Export Citation
  • Grebenyuk S.A., Perepichka I.F., Popov A.F., Evaluation of the parameters of 1:1 charge transfer complexes from spectrophotometric data by non-linear numerical method. Spectrochim. Acta A, 2002, 58, 2913-2923.

    • Crossref
    • Export Citation
  • Grimme S., Antony J., Ehrlich S., Krieg H.A., consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys., 2010, 132, 154104.

    • Crossref
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  • Kasprzak M.M., Erxleben A., Ochocki J., Properties and applications of flavonoid metal complexes. RSC Adv., 2015, 5, 45853-45877.

    • Crossref
    • Export Citation
  • Kopacz M., Quercetin- and Morinsulfonates as Analytical Reagents. J. Anal. Chem., 2003, 3, 258-262.

  • Kuzniar A., Kopacz M., Nowak D., Characterization and spectroscopic study of new complexes of Cd(II), Hg(II) and Pb(II) with the sodium salt of morin-5′-sulfonic acid. J. Coord. Chem., 2008, 61, 1005-1018.

    • Crossref
    • Export Citation
  • Leggett D.J., Computational Methods for the Determination of Formation Constants. Plenum Press, New York, USA, 1985.

  • Lutoshkin M.A., Kazachenko A.S., Assessment of various density functionals and solvation models to describe acid-base, spectral and complexing properties of thiobarbituric and barbituric acids in aqueous solution. J. Comput. Methods Sci. Eng., 2017, 17, 851-863.

  • Malesev D., Kuntic V., Investigation of metal-flavonoid chelates and the determination of flavonoids via metal-flavonoid complexing reactions, J. Serb. Chem. Soc., 2007, 72, 921-939.

    • Crossref
    • Export Citation
  • Marenich A.V., Cramer C.J., Truhlar D.G., Universal salvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B, 2009, 113, 6378-6396.

    • Crossref
    • Export Citation
  • Panche A.N., Diwan A.D., Chandra S.R., Flavonoids: an overview. J. Nutr. Sci., 2016, 5, 1-15.

  • Pietta P.G., Flavonoids as antioxidants. J. Nat. Prod., 2000, 63, 1035-1042.

  • Parr J., Some recent coordination chemistry of lead(ll). Polyhedron, 1997, 16, 551-556.

    • Crossref
    • Export Citation
  • Petrov A.I., Lutoshkin M.A., Taydakov I.V., Aqueous Complexation of YIII LaIII NdIII SmIII EuIII and YbIII with some heterocyclic substituted β-diketones. Europ. J. Inorg. Chem., 2015, 6, 1074-1082.

  • Samsonowicz M., Regulska E., Spectroscopic study of molecular structure, antioxidant activity and biological effects of metal hydroxyflavonol complexes. Spectrochim. Acta A, 2017, 73, 757-771.

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    • Crossref
    • Export Citation
  • de Souza F.V., De Giovani W.F., Antioxidant properties of complexes of flavonoids with metal ions. Redox Rep., 2013, 9, 97-104.

  • Stalin S., Sridharan K., Venkappayya D., Swaminathan S., Uma M.K., Flavonoid–Metal Ion Complexes: A Novel Class of Therapeutic Agents. Med. Res. Rev., 2014, 34, 677-702.

    • Crossref
    • PubMed
    • Export Citation
  • Vukovic S., Hay B.P., Bryantsev V.S., Predicting stability constants for uranyl complexes using density functional theory. Theor. Inorg. Chem., 2015, 54, 3995-4001.

    • Crossref
    • Export Citation
  • Wander M., Clark A., Hydration Properties of Aqueous Pb(II) Ion. Inorg. Chem., 2008, 47, 8233-8241.

    • Crossref
    • PubMed
    • Export Citation
  • Weigend F., Ahlrichs R., Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys. Chem. Chem. Phys., 2005, 7, 3297-3305.

    • Crossref
    • PubMed
    • Export Citation

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  • Adamo C., Barone V., Toward reliable density functional methods without adjustable parameters: The PBE0 model. J. Chem. Phys., 1999, 110, 6158-6170.

    • Crossref
    • Export Citation
  • Batra P., Sharma A.K., Anti-cancer potential of flavonoids: recent trends and future perspectives. 3 Biotech., 2013, 3, 439-459.

    • PubMed
    • Export Citation
  • Bryantsev V.S., Mamadou S.D., Goddard III W.A., Calculation of solvation free energies of charged solutes using mixed cluster/ continuum models. J. Phys. Chem. B., 2008, 112, 9709-9719.

    • Crossref
    • PubMed
    • Export Citation
  • Bujonek B., Kopacz M., Novak D., Lead(II) and cadmium(II) complexes with quercetin-5′-sulfonic acid and sodium morin-5′-sulfonate. Russ. J. Gen. Chem., 1996, 66, 1037-1039.

  • Casale A., De Robertis A., De Stefano C., Gianguzza A., Patan G., Rigano C., et al., Thermodynamic parameters for the formation of glycine complexes with magnesium(II), calcium(II), lead(II), manganese(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) at different temperatures and ionic strengths, with particular reference to natural fluid conditions. Thermochim. Acta, 1995, 255, 109-141.

  • Cruywagen J.J., van de Water R.F., The hydrolysis of lead(II). A potentiometric and enthalpimetric study. Talanta, 1993, 40, 1091-1095.

    • Crossref
    • Export Citation
  • Cushnie T.P., Lamb A.J., Antimicrobial activity of flavonoids. Int. J. Antimicrob. Ag., 2005, 26, 343-356.

    • Crossref
    • Export Citation
  • Eliseeva S.V., Bünzli J.-C.G., Rare earths: jewels for functional materials of the future. New J. Chem., 2011, 35, 1165.

    • Crossref
    • Export Citation
  • Grebenyuk S.A., Perepichka I.F., Popov A.F., Evaluation of the parameters of 1:1 charge transfer complexes from spectrophotometric data by non-linear numerical method. Spectrochim. Acta A, 2002, 58, 2913-2923.

    • Crossref
    • Export Citation
  • Grimme S., Antony J., Ehrlich S., Krieg H.A., consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys., 2010, 132, 154104.

    • Crossref
    • PubMed
    • Export Citation
  • Kasprzak M.M., Erxleben A., Ochocki J., Properties and applications of flavonoid metal complexes. RSC Adv., 2015, 5, 45853-45877.

    • Crossref
    • Export Citation
  • Kopacz M., Quercetin- and Morinsulfonates as Analytical Reagents. J. Anal. Chem., 2003, 3, 258-262.

  • Kuzniar A., Kopacz M., Nowak D., Characterization and spectroscopic study of new complexes of Cd(II), Hg(II) and Pb(II) with the sodium salt of morin-5′-sulfonic acid. J. Coord. Chem., 2008, 61, 1005-1018.

    • Crossref
    • Export Citation
  • Leggett D.J., Computational Methods for the Determination of Formation Constants. Plenum Press, New York, USA, 1985.

  • Lutoshkin M.A., Kazachenko A.S., Assessment of various density functionals and solvation models to describe acid-base, spectral and complexing properties of thiobarbituric and barbituric acids in aqueous solution. J. Comput. Methods Sci. Eng., 2017, 17, 851-863.

  • Malesev D., Kuntic V., Investigation of metal-flavonoid chelates and the determination of flavonoids via metal-flavonoid complexing reactions, J. Serb. Chem. Soc., 2007, 72, 921-939.

    • Crossref
    • Export Citation
  • Marenich A.V., Cramer C.J., Truhlar D.G., Universal salvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B, 2009, 113, 6378-6396.

    • Crossref
    • Export Citation
  • Panche A.N., Diwan A.D., Chandra S.R., Flavonoids: an overview. J. Nutr. Sci., 2016, 5, 1-15.

  • Pietta P.G., Flavonoids as antioxidants. J. Nat. Prod., 2000, 63, 1035-1042.

  • Parr J., Some recent coordination chemistry of lead(ll). Polyhedron, 1997, 16, 551-556.

    • Crossref
    • Export Citation
  • Petrov A.I., Lutoshkin M.A., Taydakov I.V., Aqueous Complexation of YIII LaIII NdIII SmIII EuIII and YbIII with some heterocyclic substituted β-diketones. Europ. J. Inorg. Chem., 2015, 6, 1074-1082.

  • Samsonowicz M., Regulska E., Spectroscopic study of molecular structure, antioxidant activity and biological effects of metal hydroxyflavonol complexes. Spectrochim. Acta A, 2017, 73, 757-771.

  • Schmidt M.W., Baldridge K.K., Boatz J.A., Elbert S.T., Gordon M.S., Jensen J.H., et al., General atomic and molecular electronic structure system. Comput. Chem., 1993, 14, 1347-1363.

    • Crossref
    • Export Citation
  • de Souza F.V., De Giovani W.F., Antioxidant properties of complexes of flavonoids with metal ions. Redox Rep., 2013, 9, 97-104.

  • Stalin S., Sridharan K., Venkappayya D., Swaminathan S., Uma M.K., Flavonoid–Metal Ion Complexes: A Novel Class of Therapeutic Agents. Med. Res. Rev., 2014, 34, 677-702.

    • Crossref
    • PubMed
    • Export Citation
  • Vukovic S., Hay B.P., Bryantsev V.S., Predicting stability constants for uranyl complexes using density functional theory. Theor. Inorg. Chem., 2015, 54, 3995-4001.

    • Crossref
    • Export Citation
  • Wander M., Clark A., Hydration Properties of Aqueous Pb(II) Ion. Inorg. Chem., 2008, 47, 8233-8241.

    • Crossref
    • PubMed
    • Export Citation
  • Weigend F., Ahlrichs R., Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys. Chem. Chem. Phys., 2005, 7, 3297-3305.

    • Crossref
    • PubMed
    • Export Citation
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    The UV–Vis spectra and absorbance at single wavelength (404 nm) for Pb2+-Morin system; C(Morin) = 6.87·10-5 M; pH=2.80, I=0.5 M.

  • View in gallery

    The pH-logK’ relationship for Pb2+-MSA (1) and Pb2+-morin (2) systems.

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    The keto-enol equilibria for Pb2+-morin (R=H) and Pb2+-MSA (R=HSO3).

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    The optimization geometry for morin-Pb (B) and MSA-Pb (A).

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    Thermodynamic cycle for the calculation of logKcalc.