title: 3-D structural modeling of humic acids through experimental characterization, computer assisted structure elucidation and atomistic simulations. 1. Chelsea soil humic acid.
abstract: This paper describes an integrated experimental and computational framework for developing 3-D structural models for humic acids (HAs). This approach combines experimental characterization, computer assisted structure elucidation (CASE), and atomistic simulations to generate all 3-D structural models or a representative sample of these models consistent with the analytical data and bulk thermodynamic/structural properties of HAs. To illustrate this methodology, structural data derived from elemental analysis, diffuse reflectance FT-IR spectroscopy, 1-D/2-D 1H and 13C solution NMR spectroscopy, and electrospray ionization quadrupole time-of-flight mass spectrometry (ESI QqTOF MS) are employed as input to the CASE program SIGNATURE to generate all 3-D structural models for Chelsea soil humic acid (HA). These models are subsequently used as starting 3-D structures to carry out constant temperature-constant pressure molecular dynamics simulations to estimate their bulk densities and Hildebrand solubility parameters. Surprisingly, only a few model isomers are found to exhibit molecular compositions and bulk thermodynamic properties consistent with the experimental data. The simulated 13C NMR spectrum of an equimolar mixture of these model isomers compares favorably with the measured spectrum of Chelsea soil HA.
authors.affiliation: Materials and Process Simulation Center, Beckman Institute 139-74, California Institute of Technology, Pasadena, California 91125, USA. diallo@wag.caltech.edu
authors.forename: Mamadou S
authors.initials: MS
authors.lastname: Diallo
authors.forename: Andre
authors.initials: A
authors.lastname: Simpson
authors.forename: Paul
authors.initials: P
authors.lastname: Gassman
authors.forename: Jean Loup
authors.initials: JL
authors.lastname: Faulon
authors.forename: James H
authors.initials: JH
authors.lastname: Johnson
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.forename: Patrick G
authors.initials: PG
authors.lastname: Hatcher
mesh_terms: D006812:Humic Substances / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D011312:Pressure; D012987:Soil; D017550:Spectroscopy, Fourier Transform Infrared; D013696:Temperature
chemical_list: D006812:Humic Substances; D012987:Soil