Amichetti Milagros, Franco Bruno A, Zanardi María Marta, Sarotti Ariel M
Instituto de Química Rosario, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario - CONICET, Rosario, Argentina.
Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada (INGEBIO), Facultad de Química e Ingeniería del Rosario, Pontificia Universidad Católica Argentina, Rosario, Argentina.
Magn Reson Chem. 2025 Jan;63(1):74-85. doi: 10.1002/mrc.5491. Epub 2024 Oct 30.
The application of quantum-based NMR methods for the structural elucidation of natural and unnatural products has grown significantly. However, accurately calculating the conformational landscape of flexible molecules with intricate intramolecular hydrogen bonding (IHB) networks continues to be a major challenge. In this work, we thoroughly studied the effect of entropic contributions (trough Gibbs free energies calculations) in the DP4+ performance. Our results show that to solve biased systems with strong IHB interactions requires computing the Boltzmann contributions using Gibbs free energies computed with at least triple-ξ basis set and SMD solvation model. In response to this finding, we have updated our DP4+App, a user-friendly Python applet that automates the entire process of calculating DP4+ probabilities. In the new version, the program allows for calculating of conformational contributions at any selected theory level, using either SCF or Gibbs free energies.
基于量子的核磁共振方法在天然和非天然产物结构解析中的应用有了显著增长。然而，准确计算具有复杂分子内氢键（IHB）网络的柔性分子的构象态势仍然是一项重大挑战。在这项工作中，我们通过吉布斯自由能计算深入研究了熵贡献对DP4 +性能的影响。我们的结果表明，要解决具有强IHB相互作用的偏差系统，需要使用至少三重ζ基组和SMD溶剂化模型计算的吉布斯自由能来计算玻尔兹曼贡献。基于这一发现，我们更新了DP4 +应用程序，这是一个用户友好的Python小程序，可自动执行计算DP4 +概率的整个过程。在新版本中，该程序允许使用SCF或吉布斯自由能在任何选定的理论水平上计算构象贡献。
