An Interesting Class of Porous Polymer—Revisiting the Structure of Mesoporous α‐d‐Polysaccharide Gels. Issue 3 (19th January 2016)

• Record Type: Journal Article
• Authors: White, Robin J.; Shuttleworth, Peter S.; Budarin, Vitaliy L.; Bruyn, Mario De; Fischer, Anna; Clark, James H.
• Is Part Of: ChemSusChem. Volume 9:Issue 3(2016:Feb.)
• Page Start: 280
• Page End: 288
• Publication Date: 2016-01-19
• Subjects: chiral -- diffusion -- polysaccharides -- porosity -- xerogels; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201501354
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: The processes involved in the transformation of non‐porous, native polysaccharides to their highly porous equivalents introduce significant molecular complexity and are not yet fully understood. In this paper, we propose that distinct changes in polysaccharide local short‐range ordering promotes and directs the formation of meso‐ and micro‐pores, which are investigated here using N2 sorption, FTIR, and solid‐state 13 C NMR. It is found that an increase in the overall double helical amylose content, and their local association structures, are responsible for formation of the porous polysaccharide gel phase. An exciting consequence of this local ordering change is elegantly revealed using a 19 F NMR experiment, which identifies the stereochemistry‐dependent diffusion of a fluorinated chiral probe molecule (1‐phenyl‐2, 2, 2‐trifluoroethanol) from the meso‐ to the micro‐pore region. This finding opens opportunities in the area of polysaccharide‐based chiral stationary phases and asymmetric catalyst preparation. Abstract : In a spin : A combined spectroscopic approach to the unravelling of the polysaccharide organization in mesoporous xerogels reveals a unique chiral diffusion character reflective of the assembly of amylose double helices. The results demonstrate the unique nature of porous polysaccharide‐derived materials, exemplified by an amylose‐based system, offering vast potential for a number of high value applications, such as asymmetric catalysis and chiral separation science.