@article{2d6a3a88e13e4d8aadfcfda2e1b42017,
title = "Mechanistic insight into biopolymer induced iron oxide mineralization through quantification of molecular bonding",
abstract = "Microbial production of iron (oxyhydr)oxides on polysaccharide rich biopolymers occurs on such a vast scale that it impacts the global iron cycle and has been responsible for major biogeochemical events. Yet the physiochemical controls these biopolymers exert on iron (oxyhydr)oxide formation are poorly understood. Here we used dynamic force spectroscopy to directly probe binding between complex, model and natural microbial polysaccharides and common iron (oxyhydr)oxides. Applying nucleation theory to our results demonstrates that if there is a strong attractive interaction between biopolymers and iron (oxyhydr)oxides, the biopolymers decrease the nucleation barriers, thus promoting mineral nucleation. These results are also supported by nucleation studies and density functional theory. Spectroscopic and thermogravimetric data provide insight into the subsequent growth dynamics and show that the degree and strength of water association with the polymers can explain the influence on iron (oxyhydr)oxide transformation rates. Combined, our results provide a mechanistic basis for understanding how polymer-mineral-water interactions alter iron (oxyhydr)oxides nucleation and growth dynamics and pave the way for an improved understanding of the consequences of polymer induced mineralization in natural systems. This journal is ",
author = "Sand, {K. K.} and S. Jelavi{\'c} and S. Dobbersch{\"u}tz and P.D. Ashby and M.J. Marshall and K. Dideriksen and S.L.S. Stipp and S.N. Kerisit and R.W. Friddle and J.J. Deyoreo",
note = "Funding Information: We sincerely thank Dr Halei Zhai, Dr Jinhui Tao and Dr Chris-tina Newcomb for helpful discussion on DFS, Kirstine Bach for generation of 3D gures and renderings, Dr Nico Bovet for useful comments on cryoXPS, Dr Glen Waychunas for providing the hematite sample and Dr Caroline Ajo-Franklin and Dr Kevin Rosso for encouragement and intellectual input. Funding for data collection and interpretation and for molecular simulations was provided by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences (OBES), Chemical Sciences, Geosciences and Biosciences Division through its Geosciences Program at Pacic Northwest National Laboratory (PNNL), which is operated by Battelle for the U.S. DOE under Contract DE-AC05-76RL01830. Analytical method development was supported by Sandia National Laboratories, a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. The research was performed using the Environmental and Molecular Sciences Laboratory, which is a DOE Office of Science Scientic User Facility (SUF) sponsored by the Office of Biological and Environmental Research operated by PNNL, under proposal 48274 and a U.S. DOE Office of Science Early Career Award (Project 60385). This research also used resources of U.S. DOE OBES SUFs, the Advanced Photon Source and the Molecular Foundry, which are operated for the DOE OBES by, respectively, Argonne National Laboratory under Contract No. DE-AC02-06CH11357 and LBNL under Contract No. DE-AC02-05CH11231. SJ, SD, KD and SLSS were supported by the running budget of the Materials Chemistry Research Section, University of Copenhagen. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",
year = "2020",
month = aug,
doi = "10.1039/d0na00138d",
language = "English",
volume = "2",
pages = "3323--3333",
journal = "Nanoscale Advances",
issn = "2516-0230",
publisher = "Royal Society of Chemistry",
number = "8",
}