title: Intermolecular interactions and 3D structure in cellulose-NaOH-urea aqueous system.
abstract: The dissolution of cellulose in NaOH/urea aqueous solution at low temperature is a key finding in cellulose science and technology. In this paper, (15)N and (23)Na NMR experiments were carried out to clarify the intermolecular interactions in cellulose/NaOH/urea aqueous solution. It was found that there are direct interactions between OH(-) anions and amino groups of urea through hydrogen bonds and no direct interaction between urea and cellulose. Moreover, Na(+) ions can interact with both cellulose and urea in an aqueous system. These interactions lead to the formation of cellulose-NaOH-urea-H2O inclusion complexes (ICs). (23)Na relaxation results confirmed that the formation of urea-OH(-) clusters can effectively enhance the stability of Na(+) ions that attracted to cellulose chains. Low temperature can enhance the hydrogen bonding interaction between OH(-) ions and urea and improve the binding ability of the NaOH/urea/H2O clusters that attached to cellulose chains. Cryo-TEM observation confirmed the formation of cellulose-NaOH-urea-H2O ICs, which is in extended conformation with mean diameter of about 3.6 nm and mean length of about 300 nm. Possible 3D structure of the ICs was proposed by the M06-2X/6-31+G(d) theoretical calculation, revealing the O3H···O5 intramolecular hydrogen bonds could remain in the ICs. This work clarified the interactions in cellulose/NaOH/urea aqueous solution and the 3D structure of the cellulose chain in dilute cellulose/NaOH/urea aqueous solution.
authors.affiliation: State Key Laboratory of Polymer Physics and Chemistry, Beijing National Laboratory of Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
authors.forename: Zhiwei
authors.initials: Z
authors.lastname: Jiang
authors.forename: Yan
authors.initials: Y
authors.lastname: Fang
authors.forename: Junfeng
authors.initials: J
authors.lastname: Xiang
authors.forename: Yanping
authors.initials: Y
authors.lastname: Ma
authors.forename: Ang
authors.initials: A
authors.lastname: Lu
authors.forename: Hongliang
authors.initials: H
authors.lastname: Kang
authors.forename: Yong
authors.initials: Y
authors.lastname: Huang
authors.forename: Hongxia
authors.initials: H
authors.lastname: Guo
authors.forename: Ruigang
authors.initials: R
authors.lastname: Liu
authors.forename: Lina
authors.initials: L
authors.lastname: Zhang
mesh_terms: D002482:Cellulose / Q000737:chemistry* / Q000378:metabolism; D055598:Chemical Phenomena; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D012972:Sodium Hydroxide / Q000737:chemistry* / Q000378:metabolism; D014508:Urea / Q000737:chemistry* / Q000378:metabolism; D014867:Water / Q000737:chemistry* / Q000378:metabolism
chemical_list: D014867:Water; D012972:Sodium Hydroxide; D014508:Urea; D002482:Cellulose