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- (GD3)38 to account for long-range van der Waals interactions. The computations of peptide and complex
- Table 1. Electronic energy differences (ΔΕ) in kcal/mol between the most stable configuration of HgS(e)AVP
- than the most stable compact forms, with 3-, 4-, and 5-Se exceeding by up to 32.8 kcal/mol a trend also
- results in the cage-like 2-S configuration emerging as the most stable structure, lying 1.6 kcal/mol lower in
- protons disrupts hydrogen bonding, resulting in structural rearrangements and stabilization of the cage-like 2-S(e)
- Table 2. Energy differences (ΔE) in kcal/mol for HgS(e)AVP complexes computed with the fourth-order Douglas-
- dissociates as a charged ion (for n=1 or 2) or as a neutral atom (for n=0). The free electrons denoted as 𝑛𝑒 −
- the HgSAVP complex is less stable than the HgSeAVP complex, whereas ΔBE < 0 implies the opposite.
- example, the 1-Se configuration appears to be more stable than the 1-S configuration in both computational
- formalism.57 For this purpose, the long-range corrected functional LC-ωHPBE was applied.
- observed difference of ~0.19 eV between the two systems corresponds to a ~53% increase relative to the S
- polarizabilities of the most stable conformers of HgSAVP and HgSeAVP. Calculations were performed using B3LYP-
- distributions, the presented NTOs account for 99% of the total transition. Excitation energies, and NTOs were
- transitions in the most stable conformers suggest that ES1 of 0-Se is analogous in character to ES2 of 0-S.
- transition dipole moment (0.43 D vs. 0.36 D) and a ~9% greater change in total dipole moment (Δμ: 9.3 D
- 𝐸strain = 𝐸peptide −𝐸complex-HgBQ (3)
- typically range between 5-15 kcal/mol60, which is considered as a sufficient threshold to influence folding
- hydrogen-bonding interactions in the most stable structures, 0-S(e), which share nearly identical compact
- analysis (Table S1, ESI), (ii) Wiberg and AIM delocalization Bond Indexes, WBI and OH, respectively,
- and σ*NH(Gly), accounting for 25.8–30.7% of stabilizing interactions, with ΔE(2) values between 26 and
- density polarization toward the chalcogen in both systems, with Se contributing 68–77% and S 70.2–77.6%.
- The atomic contribution of mercury in the NLMOs follows a similar trend, ranging from 31 to 15.2% in 0-
- Se and from 20.8 to 15.1% in 0-S, in the real system. This suggests that the metal-chalcogen bonds in the
- 0-S(e) complexes (strong covalent character). The obtained EDA results (see Table 3) confirm that both
- Specifically, ΔEorb dominates the bonding stabilization, contributing 54.1% in Se–Hg–Se and 56.5% in S–
- Hg–S. The electrostatic term (ΔEelstat) also significantly contributes to the total bonding energy (~ 40 %).
- Similarly, ΔEelstat is also very close in magnitude for both systems (43.3% in Se–Hg–Se and 40.8% in S–
- Table 3. EDA at the ZORA-B3LYP-D3(BJ)/TZ2P level was performed for the 0-S(e)′ model systems (derived from
- exhibits quasi-formed Se–Hg bonds with a maximum elongation of only 8.7% compared to the final bridged
- approximately 10.4% compared to the final bridged structure (2.410 and 2.390 Å). The shortest for Se–Hg
- stabilization energies for Se come from better orbital overlaps (see Table S4, ESI) between the lone pairs
- (NLMO) are strongly polarized toward the chalcogen, with approximately 75 % of Se/S contribution in the
- mono and bis-metalated complexes and around 65 % in the bridged complexes. The Se–Hg bonds exhibit
- a slightly more covalent character than the S–Hg bonds (see Table S5, ESI), with a higher contribution
- from the metal on the chalcogen-mercury bond. The metal contribution increases from 15 % to about 30
- of 64 kcal/mol, compared to 83 kcal/mol for its S analogue. This difference corresponds to a ~23%
- verified by RMSD distributions and by hydrogen bond analysis (Table S6), which revealed a network of
- stable intramolecular hydrogen bonds (e.g., Tyr²–Asn⁵ and Tyr²–Cys⁶) in the compact form (AVP–sg3).
- Conversely, SeAVP showed greater structural flexibility, adopting its more compact arrangement (Rg ~4.5
- Å) later (~650 ns) and exhibiting fewer stable hydrogen bonds, such as Cys⁶–Gly⁹ and Phe³–Tyr⁵. This
- interaction with an occupancy of 92% (Table S6, Figure S12E). In contrast, HgSeAVP showed increased
- interactions with Gln⁴ and Gly⁹, neither of which achieved substantial occupancy (Table S6, Figure S12F).
Methods (brief)
- geometries reflect the most stable and frequently sampled states observed during the simulations, the
- Skalny, M. Butnariu, M. Dadar, I. Sarac, J. Aaseth and G. Bjørklund, Sulfhydryl groups as
- 28 Investigation of Elemental Mass Spectrometry in Pharmacology for Peptide Quantitation at
- and C. Enjalbal, Investigation of elemental mass spectrometry in pharmacology for peptide
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