A First Principles Investigation of Histidine and its Ionic Counterparts: A DFT Study
UppulaPurushotham, HendrikZipse and G. NarahariSastry*
Center for Molecular Modeling, Indian Institute of Chemical Technology, Tarnaka,
Hyderabad - 500 007,
Table S1: The Relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) neutral histidine (with respect to H1) at various levels of theory.
Table S2: The relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) histidine zwitterions (with respect to HZ1) at various levels of theory.
Table S3: Relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) histidine cation at various levels of theory.
Table S4: The Relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) histidine anion (with respect to HA1) at various levels of theory.
Table S5: The Relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of neutral histidine (with respect to H1) at various levels of theory.
Table S6: The Relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of histidine anion at various levels of theory.
Table S7: The relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of histidine cation at various levels of theory.
Table S8: The relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of histidine zwitterions at various levels of theory.
Table S9: The relative energy (ΔE in kcal/mol) of top 10 conformations of neutral histidine two tautomer conformers at PCM-M05-2X/cc-pVTZ level of theory.
Table S10: The relative energy (ΔE in kcal/mol) of top 5 conformations of neutral histidine two tautomer conformers at MP2 and M05-2X theory with using cc-pVTZ basis set.
Table S1: The Relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) neutral histidine (with respect to H1) at various levels of theory.
Str. / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZNτH1 / 0.00 / 0.00 / 0.00
NτH2 / 0.89 / 1.71 / 1.25
NτH3 / 1.48 / 2.07 / 2.06
NτH4 / 1.66 / 2.53 / 2.25
NτH5 / 4.15 / 5.18 / 3.91
NτH6 / 4.52 / 5.30 / 4.24
NτH7 / 4.55 / 5.19 / 5.03
NτH8 / 4.65 / 4.15 / 3.48
NτH9 / 4.90 / 4.64 / 3.93
NτH10 / 5.35 / 5.74 / 4.81
NτH11 / 5.48 / 6.20 / 5.76
NτH12 / 5.60 / 6.31 / 5.43
NτH13 / 5.70 / 6.43 / 5.36
NτH14 / 5.76 / 6.23 / 4.80
NτH15 / 5.80 / 6.48 / 4.99
NτH16 / 5.91 / 6.42 / 5.40
NτH17 / 5.94 / 5.22 / 4.68
NτH18 / 6.41 / 7.32 / 6.30
NτH19 / 6.57 / 7.35 / 6.36
NτH20 / 6.61 / 7.13 / 5.67
NτH21 / 6.75 / 7.23 / 5.77
NτH22 / 6.95 / 6.53 / 5.35
NτH23 / 7.05 / 6.86 / 5.53
NτH24 / 7.16 / 7.27 / 6.03
NτH25 / 7.79 / 8.26 / 6.90
NτH26 / 7.96 / 8.42 / 7.02
NτH27 / 8.06 / 8.52 / 7.14
NτH28 / 8.30 / 8.31 / 6.95
NτH29 / 8.50 / 8.52 / 6.87
NτH30 / 8.82 / 8.55 / 7.56
NτH31 / 10.25 / 11.32 / 9.52
NτH32 / 13.40 / 13.64 / 11.42
NτH33 / 13.71 / 14.47 / 11.55
Table S2: The relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) histidine zwitterions (with respect to HZ1) at various levels of theory.
Str. / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZ / M05-2X/aug-cc-pVTZ//M05-2X/cc-pVTZ
NτHZ1 / 0.00 / 0.00 / 0.00 / 0.00
NτHZ2 / 0.23 / 0.59 / 0.65 / 0.52
NτHZ3 / 3.33 / 3.93 / 3.77 / 3.58
NτHZ4 / 4.30 / 3.66 / 4.23 / 4.15
NτHZ5 / 4.62 / 3.72 / 3.42 / 3.13
NτHZ6 / 6.38 / 6.86 / 7.57 / 7.48
NτHZ7 / 7.33 / 6.92 / 6.11 / 5.85
Table S3: Relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) histidine cation at various levels of theory.
Str. / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZNτHC1 / 0.00 / 0.00 / 0.00
NτHC2 / 0.07 / -0.42 / -0.22
NτHC3 / 2.89 / 2.75 / 3.18
NτHC4 / 8.27 / 9.56 / 8.29
NτHC5 / 8.48 / 9.16 / 7.89
NτHC6 / 9.15 / 9.75 / 8.61
NτHC7 / 9.60 / 9.69 / 8.64
NτHC8 / 14.59 / 14.72 / 14.26
NτHC9 / 15.22 / 14.85 / 14.24
NτHC10 / 15.72 / 15.35 / 15.19
NτHC11 / 19.07 / 18.45 / 18.29
Table S4: The Relative energy (ΔE in kcal/mol) of various conformations of HIS(NτH) histidine anion (with respect to HA1) at various levels of theory.
Str / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZ / M05-2X/aug-cc-pVTZ//M05-2X/cc-pVTZ
NτHA1 / 0.00 / 0.00 / 0.00 / 0.00
NτHA2 / 0.11 / -0.91 / -1.07 / -0.85
NτHA3 / 0.23 / -0.78 / -1.08 / -0.92
NτHA4 / 0.62 / 0.86 / 0.68 / 0.79
NτHA5 / 0.70 / 0.75 / 1.19 / 1.47
NτHA6 / 1.32 / 1.48 / 1.47 / 1.63
NτHA7 / 1.75 / 1.49 / 1.30 / 1.49
NτHA8 / 2.71 / 2.77 / 2.37 / 2.61
NτHA9 / 4.54 / 4.98 / 3.82 / 3.48
Table S5: The Relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of neutral histidine (with respect to H1) at various levels of theory.
Str. / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZNπH1 / 0.00 / 0.00 / 0.00
NπH2 / 1.10 / 2.38 / 2.44
NπH3 / 1.62 / 2.29 / 1.99
NπH4 / 3.29 / 3.14 / 2.50
NπH5 / 4.65 / 4.56 / 3.99
NπH6 / 4.69 / 5.18 / 4.40
NπH7 / 5.75 / 6.51 / 5.76
NπH8 / 5.96 / 6.64 / 5.51
NπH9 / 6.30 / 7.21 / 6.00
NπH10 / 6.32 / 6.62 / 5.61
NπH11 / 6.59 / 7.33 / 5.88
NπH12 / 7.44 / 8.33 / 7.25
NπH13 / 7.61 / 8.42 / 6.81
NπH14 / 7.67 / 8.70 / 6.75
NπH15 / 7.77 / 7.90 / 6.51
NπH16 / 7.95 / 8.80 / 7.18
NπH17 / 8.15 / 8.79 / 7.96
NπH18 / 8.23 / -a- / -a-
NπH19 / 8.81 / 10.07 / 9.61
NπH20 / 8.94 / 9.86 / 8.02
NπH21 / 9.35 / 9.72 / 8.69
NπH22 / 9.49 / 10.08 / 8.91
NπH23 / 9.69 / 10.41 / 8.98
NπH24 / 9.90 / 10.54 / 8.81
NπH25 / 10.30 / 11.21 / 9.79
NπH26 / 10.43 / 11.69 / 10.04
NπH27 / 10.56 / 11.03 / 9.33
NπH28 / 10.90 / 11.74 / 9.97
NπH29 / 10.94 / 10.08 / 10.38
NπH30 / 13.52 / 14.87 / 12.16
Note: -a- conformer collapsed with NπH5 conformer.
Table S6: The Relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of histidine anion at various levels of theory.
Str. / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZ / M05-2X/aug-ccpVTZ//M05-2X/cc-pVTZ
NπHA1 / 0.00 / 0.00 / 0.00 / 0.00
NπHA2 / 0.18 / 0.10 / 0.15 / 0.17
NπHA3 / 1.80 / 0.70 / 0.72 / 0.59
NπHA4 / 3.05 / 1.76 / 1.47 / 1.49
NπHA5 / 3.44 / 2.59 / 2.06 / 1.76
NπHA6 / 4.84 / 4.42 / 3.88 / 3.60
NπHA7 / 5.79 / 5.41 / 5.37 / 5.31
NπHA8 / 6.16 / 5.32 / 5.57 / 5.64
NπHA9 / 15.32 / 14.74 / 13.50 / 13.05
NπHA10 / 16.80 / 16.65 / 14.09 / 13.16
NπHA11 / 17.41 / 16.96 / 16.05 / 15.48
NπHA12 / 17.84 / 17.59 / 16.42 / 15.89
Table S7: The relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of histidine cation at various levels of theory.
Str. / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZNπHC1 / 0.00 / 0.00 / 0.00
NπHC2 / 1.75 / 2.18 / 1.59
NπHC3 / 2.11 / 1.65 / 2.09
NπHC4 / 5.34 / 5.63 / 5.61
NπHC5 / 7.48 / 8.39 / 7.61
NπHC6 / 9.46 / 10.03 / 8.74
NπHC7 / 10.35 / 11.54 / 10.16
NπHC8 / 10.56 / 12.52 / 11.06
NπHC9 / 10.87 / 11.91 / 10.12
NπHC10 / 12.16 / 12.89 / 12.51
NπHC11 / 12.78 / 13.69 / 13.67
NπHC12 / 16.82 / 17.20 / 16.22
Table S8: The relative energy (ΔE in kcal/mol) of various conformations of His(NπH) tautomer of histidine zwitterions at various levels of theory.
Str. / B3LYP/6-31G(d) / M05-2X/6-31G(d) / M05-2X/cc-pVTZ / M05-2X/aug-cc-pVTZ// M05-2X/cc-pVTZ
NπHZ1 / 0.20 / 0.00 / 0.00 / 0.00
NπHZ2 / 2.80 / 2.75 / 2.76 / 3.57
NπHZ3 / 4.97 / 5.52 / 4.06 / 8.29
NπHZ4 / 5.21 / 6.26 / 4.23 / 10.65
NπHZ5 / 6.36 / 7.59 / 5.81 / 16.50
NπHZ6 / 6.52 / 7.64 / 7.00 / 15.63
Table S9: The relative energy (ΔE in kcal/mol) of top 10 conformations of neutral histidine two tautomer conformers at PCM-M05-2X/cc-pVTZ level of theory.
Str. / M05-2X/cc-pVTZ / Str. / M05-2X/cc-pVTZNτH1 / 0.000 / NπH1 / 0.000
NτH2 / 0.550 / NπH2 / 1.360
NτH3 / 0.550 / NπH3 / 2.482
NτH4 / -0.060 / NπH4 / 3.719
NτH5 / 0.937 / NπH5 / 3.506
NτH6 / 4.525 / NπH6 / 4.713
NτH7 / 3.481 / NπH7 / 2.404
NτH8 / 3.323 / NπH8 / 2.332
NτH9 / 4.159 / NπH9 / 2.734
NτH10 / 5.405 / NπH10 / 5.839
Table S10: The relative energy (ΔE in kcal/mol) of top 5 conformations of neutral histidine two tautomer conformers at MP2 and M05-2X level of theory.
Str. / M05-2X/cc-pVTZ / MP2/cc-pVTZ / Str. / M05-2X/cc-pVTZ / MP2/cc-pVTZNτH1 / 0.000 / 0.000 / NπH1 / 0.000 / 0.560
NτH2 / 1.254 / 1.603 / NπH2 / 2.441 / 3.235
NτH3 / 2.059 / 3.063 / NπH3 / 1.986 / 3.063
NτH4 / 2.248 / 3.092 / NπH4 / 2.502 / 3.646
NτH5 / 3.907 / 4.189 / NπH5 / 3.995 / 4.795