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Bis(amino acidato)copper(II) compounds in blood plasma: a review of computed structural properties and amino acid affinities for Cu2+ informing further pharmacological research Cover

Bis(amino acidato)copper(II) compounds in blood plasma: a review of computed structural properties and amino acid affinities for Cu2+ informing further pharmacological research

Archives of Industrial Hygiene and Toxicology
Volume 75 (2024): Issue 3 (September 2024)
By: Jasmina Sabolović  
Open Access
|Sep 2024

Figures & Tables

Figure 1

Schematic diagrams of five amino acids. Uncommon atom symbols: Cc – carboxylato group carbon; Cad – amido group carbon; Nam – amino group nitrogen; Nad – amido group nitrogen; Oad – amido group oxygen; Oh – hydroxyl group oxygen. Donor atoms for binding with metal ions are denoted by violet and yellow circles as follows: amino Nam and carboxylato O atoms common to all amino acids (violet), and side-chain atoms specific for each amino acid (yellow)
Schematic diagrams of five amino acids. Uncommon atom symbols: Cc – carboxylato group carbon; Cad – amido group carbon; Nam – amino group nitrogen; Nad – amido group nitrogen; Oad – amido group oxygen; Oh – hydroxyl group oxygen. Donor atoms for binding with metal ions are denoted by violet and yellow circles as follows: amino Nam and carboxylato O atoms common to all amino acids (violet), and side-chain atoms specific for each amino acid (yellow)

Figure 2

B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His)2 conformers in the glycine- (G) and histamine-like (H) His coordination modes with a trans (t) or cis (c) configuration, along with their relative Gibbs free energies (∆Gwater, kJ/mol)
B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His)2 conformers in the glycine- (G) and histamine-like (H) His coordination modes with a trans (t) or cis (c) configuration, along with their relative Gibbs free energies (∆Gwater, kJ/mol)

Figure 3

B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Asn) conformers with His in the glycine- (G) and histamine-like (H) coordination and Asn in the glycine-like mode (N) with a trans (t) or cis (c) configurations along with their relative Gibbs free energies (∆Gwater, kJ/mol)
B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Asn) conformers with His in the glycine- (G) and histamine-like (H) coordination and Asn in the glycine-like mode (N) with a trans (t) or cis (c) configurations along with their relative Gibbs free energies (∆Gwater, kJ/mol)

Figure 4

B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Gln) conformers with His in the glycine- (G) and histamine-like (H) modes and Gln in the glycine-like mode (Q) in a trans (t) or cis (c) configurations, along with their relative Gibbs free energies (∆Gwater, kJ/mol)
B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Gln) conformers with His in the glycine- (G) and histamine-like (H) modes and Gln in the glycine-like mode (Q) in a trans (t) or cis (c) configurations, along with their relative Gibbs free energies (∆Gwater, kJ/mol)

Figure 5

B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Thr) conformers with His in the glycine- (G) and histamine-like (H) modes and Thr in the glycinato mode (T) in a trans (t) or cis (c) configurations along with their relative Gibbs free energies (∆Gwater, kJ/mol)
B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Thr) conformers with His in the glycine- (G) and histamine-like (H) modes and Thr in the glycinato mode (T) in a trans (t) or cis (c) configurations along with their relative Gibbs free energies (∆Gwater, kJ/mol)

Figure 6

B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Cys) conformers in a trans (t) or cis (c) configurations with His in the glycinato (G) and histaminato (H) mode and with Cys in the glycinato (NO, left) and NS mode (right; Nam and S as the donor atoms), along with the relative Gibbs free energies (∆Gwater, kJ/mol)
B3LYP-D3/6-311+G(3df,2p) prediction of aqueous Cu(His) (Cys) conformers in a trans (t) or cis (c) configurations with His in the glycinato (G) and histaminato (H) mode and with Cys in the glycinato (NO, left) and NS mode (right; Nam and S as the donor atoms), along with the relative Gibbs free energies (∆Gwater, kJ/mol)

Figure 7

Metal ion affinity (MIA) values calculated for low-energy aqueous conformers of five Cu(aa)2 compounds obtained using the B3LYP-D3 functional and 6-311+G(3df,2p) basis set (see Table 2). [Cu(His)(Gln) and Cu(His) (Cys) values are based on two earlier reports (43, 44)]
Metal ion affinity (MIA) values calculated for low-energy aqueous conformers of five Cu(aa)2 compounds obtained using the B3LYP-D3 functional and 6-311+G(3df,2p) basis set (see Table 2). [Cu(His)(Gln) and Cu(His) (Cys) values are based on two earlier reports (43, 44)]

Experimentally determined stability constants (log β) of ternary and binary amino acidato copper(II) compounds determined potentiometrically (37 °C, 0_15 mol/L NaClO4)

Ternary compoundslog βReference
Cu(His)(Gln)16.70353
Cu(His)(Thr)17.03051
Cu(His)(Asn)16.75653
Cu(His)(Cys)*16.960

Enthalpies and metal ion affinities (MIA) for selected Cu(His)2, Cu(His)(Asn), and Cu(His)(Thr) conformers and their corresponding His−, Asn−, and Thr− minimum structures calculated using the B3LYP-D3 functional and 6-311+G(3df,2p) basis set in implicitly modelled aqueous solution using polarisable continuum model (PCM) at 298_15 K

Conformer*Enthalpy (a.u.)MIA (kJ/mol)
Cu(His)2L1− (His−)L2− (His−)
tGG−2737.094653−548.382771−548.384674979.6
cGG−2737.096348−548.382743−548.382719989.3
tHH−2737.091682−548.382725−548.384669971.9
cHH−2737.092565−548.383451−548.384666972.4
tHG−2737.095356−548.382781−548.382751986.5
cHG−2737.095784−548.382817−548.384681982.4
Cu(His)(Asn)L1− (His−)L2− (Asn−)
tGN−2680.789917−548.382752−492.082518972.9
cGN−2680.786351−548.382801−492.080036969.9
cHN (1)−2680.792287−548.382750−492.080519984.4
cHN (2)−2680.787487−548.382733−492.080062973.0
tHN−2680.788118−548.382752−492.082536968.1
Cu(His)(Thr)L1− (His−)L2− (Thr−)
tGT (1)−2626.583463−548.382793−437.873675979.1
tTG (2)−2626.583989−548.382791−437.880005963.8
cGT−2626.581558−548.382725−437.873662974.3
tHT (1)−2626.581712−548.382770−437.873628974.6
tHT (2)−2626.583521−548.382751−437.880002962.7
cHT−2626.588520−548.382757−437.879386977.4
DOI: https://doi.org/10.2478/aiht-2024-75-3871 | Journal eISSN: 1848-6312 | Journal ISSN: 0004-1254
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Language: English, Croatian, Slovenian
Page range: 159 - 171
Submitted on: Jun 1, 2024
|
Accepted on: Jun 1, 2024
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Published on: Sep 29, 2024
Published by: Institute for Medical Research and Occupational Health
In partnership with: Paradigm Publishing Services
Publication frequency: 4 issues per year
Keywords:
conformation,
density functional theory calculations,
hydrogen bonding,
polar amino acids,
trace transition metal
Related subjects:
Medicine,
Basic medical science,
Basic medical science, other

© 2024 Jasmina Sabolović, published by Institute for Medical Research and Occupational Health
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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