PMID- 30850608
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20190326
LR  - 20200309
IS  - 2041-1723 (Electronic)
IS  - 2041-1723 (Linking)
VI  - 10
IP  - 1
DP  - 2019 Mar 8
TI  - Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar 
      aprotic solvents.
PG  - 1132
LID - 10.1038/s41467-019-09090-4 [doi]
LID - 1132
AB  - The use of polar aprotic solvents in acid-catalyzed biomass conversion reactions 
      can lead to improved reaction rates and selectivities. We show that further 
      increases in catalyst performance in polar aprotic solvents can be achieved 
      through the addition of inorganic salts, specifically chlorides. Reaction 
      kinetics studies of the Bronsted acid-catalyzed dehydration of fructose to 
      hydroxymethylfurfural (HMF) show that the use of catalytic concentrations of 
      chloride salts leads to a 10-fold increase in reactivity. Furthermore, increased 
      HMF yields can be achieved using polar aprotic solvents mixed with chlorides. Ab 
      initio molecular dynamics simulations (AIMD) show that highly localized negative 
      charge on Cl(-) allows the chloride anion to more readily approach and stabilize 
      the oxocarbenium ion that forms and the deprotonation transition state. High 
      concentrations of polar aprotic solvents form local hydrophilic environments near 
      the reactive hydroxyl group which stabilize both the proton and chloride anions 
      and promote the dehydration of fructose.
FAU - Mellmer, Max A
AU  - Mellmer MA
AD  - Department of Chemical and Biological Engineering, University of 
      Wisconsin-Madison, Madison, WI, 53706, USA.
AD  - DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, 
      Madison, WI, 53706, USA.
FAU - Sanpitakseree, Chotitath
AU  - Sanpitakseree C
AD  - Department of Chemical Engineering and Materials Science, University of 
      Minnesota, Minneapolis, MN, 55455, USA.
FAU - Demir, Benginur
AU  - Demir B
AUID- ORCID: 0000-0003-3469-906X
AD  - Department of Chemical and Biological Engineering, University of 
      Wisconsin-Madison, Madison, WI, 53706, USA.
AD  - DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, 
      Madison, WI, 53706, USA.
FAU - Ma, Kaiwen
AU  - Ma K
AD  - Department of Chemical and Biological Engineering, University of 
      Wisconsin-Madison, Madison, WI, 53706, USA.
FAU - Elliott, William A
AU  - Elliott WA
AD  - Department of Chemical Engineering, Pennsylvania State University, State College, 
      PA, 16801, USA.
FAU - Bai, Peng
AU  - Bai P
AUID- ORCID: 0000-0002-6881-4663
AD  - Department of Chemical Engineering and Materials Science, University of 
      Minnesota, Minneapolis, MN, 55455, USA.
FAU - Johnson, Robert L
AU  - Johnson RL
AD  - Department of Chemical and Biological Engineering, Iowa State University, Ames, 
      IA, 50011, USA.
FAU - Walker, Theodore W
AU  - Walker TW
AD  - Department of Chemical and Biological Engineering, University of 
      Wisconsin-Madison, Madison, WI, 53706, USA.
FAU - Shanks, Brent H
AU  - Shanks BH
AD  - Department of Chemical and Biological Engineering, Iowa State University, Ames, 
      IA, 50011, USA.
FAU - Rioux, Robert M
AU  - Rioux RM
AD  - Department of Chemical Engineering, Pennsylvania State University, State College, 
      PA, 16801, USA.
AD  - Department of Chemistry, Pennsylvania State University, State College, PA, 16801, 
      USA.
FAU - Neurock, Matthew
AU  - Neurock M
AD  - Department of Chemical Engineering and Materials Science, University of 
      Minnesota, Minneapolis, MN, 55455, USA.
FAU - Dumesic, James A
AU  - Dumesic JA
AUID- ORCID: 0000-0001-6542-0856
AD  - Department of Chemical and Biological Engineering, University of 
      Wisconsin-Madison, Madison, WI, 53706, USA. jdumesic@wisc.edu.
AD  - DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, 
      Madison, WI, 53706, USA. jdumesic@wisc.edu.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
PT  - Research Support, U.S. Gov't, Non-P.H.S.
DEP - 20190308
PL  - England
TA  - Nat Commun
JT  - Nature communications
JID - 101528555
PMC - PMC6408490
COIS- The authors declare no competing interests.
EDAT- 2019/03/10 06:00
MHDA- 2019/03/10 06:01
PMCR- 2019/03/08
CRDT- 2019/03/10 06:00
PHST- 2018/09/25 00:00 [received]
PHST- 2019/02/19 00:00 [accepted]
PHST- 2019/03/10 06:00 [entrez]
PHST- 2019/03/10 06:00 [pubmed]
PHST- 2019/03/10 06:01 [medline]
PHST- 2019/03/08 00:00 [pmc-release]
AID - 10.1038/s41467-019-09090-4 [pii]
AID - 9090 [pii]
AID - 10.1038/s41467-019-09090-4 [doi]
PST - epublish
SO  - Nat Commun. 2019 Mar 8;10(1):1132. doi: 10.1038/s41467-019-09090-4.