Enzymatically produced nano-ordered short elements containing cellulose Iβ crystalline domains

This paper reports an attempt to characterize the residues extracted after enzymatic hydrolysis of Cladophora microcrystalline cellulose comprising two crystalline allomorphs of cellulose, Ia and Ib. Cellulose Ia is preferentially hydrolyzed by Trichoderma cellulase (Hayashi, Ishihara, Sugiyama, & Okano, 1998a). This selective hydrolysis process produced short elements. X-ray diffraction, electron diffraction and FT-IR analyses revealed that these short elements were highly crystalline, similar to the untreated microcrystalline cellulose, and mostly consisted of the Ib phase. The length distribution of the crystalline elements was ca. 350 nm. Furthermore, the average length of 350 nm corresponded to the degree of polymerization of 690 for b-glucan chains obtained by size exclusion chromatographic analysis. The close agreement indicates that individual molecular chains may be extended in the longitudinal direction of the obtained crystalline element. These characteristic short elements have the potential to act as nano-ordered particles and may be useful as fillers to enhance the mechanical properties of various materials. q 2005 Elsevier Ltd. All rights reserved.

[1]  J. Sugiyama,et al.  Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall , 1991 .

[2]  J. Sugiyama,et al.  Transformation of Valonia cellulose crystals by an alkaline hydrothermal treatment , 1990 .

[3]  J. Sugiyama,et al.  Unidirectional processive action of cellobiohydrolase Cel7A on Valonia cellulose microcrystals , 1998, FEBS letters.

[4]  B. Henrissat,et al.  Imaging the Enzymatic Digestion of Bacterial Cellulose Ribbons Reveals the Endo Character of the Cellobiohydrolase Cel6A from Humicola insolens and Its Mode of Synergy with Cellobiohydrolase Cel7A , 2000, Applied and Environmental Microbiology.

[5]  R. Atalla,et al.  Native Cellulose: A Composite of Two Distinct Crystalline Forms , 1984, Science.

[6]  R. Brown,et al.  Acid hydrolysis behaviour of microbial cellulose II , 1995 .

[7]  P. B. Marsh.  Microscopic Observations on Cotton Fibers Subjected to Enzymatic Degradation , 1957 .

[8]  Rajai H. Atalla,et al.  Studies of microstructure in native celluloses using solid-state carbon-13 NMR , 1984 .

[9]  K. W. King.  Enzymic degradation of crystalline hydrocellulose. , 1966, Biochemical and Biophysical Research Communications - BBRC.

[10]  Junji Sugiyama,et al.  Selective degradation of the cellulose Iα component in Cladophora cellulose with Trichoderma viride cellulase , 1997 .

[11]  G. Halliwell.  Solubilization of native and derived forms of cellulose by cell-free microbial enzymes. , 1966, The Biochemical journal.

[12]  J. Sugiyama,et al.  The Iα →Iβ transformation of highly crystalline cellulose by annealing in various mediums , 1991 .

[13]  B. Henrissat.  Enzymatic cellulose degradation , 1998 .

[14]  J. Sugiyama,et al.  Combined infrared and electron diffraction study of the polymorphism of native celluloses , 1991 .

[15]  G. Halliwell,et al.  The formation of short fibres from native cellulose by components of Trichoderma koningii cellulase. , 1970, The Biochemical journal.

[16]  H. Bochem,et al.  Formation of cross-fractures in cellulose microfibril structure by an endoglucanase-cellobiohydrolase complex from Trichoderma reesei. , 1993, FEMS microbiology letters.

[17]  J. Sugiyama,et al.  The enzymatic susceptibility of cellulose microfibrils of the algal-bacterial type and the cotton-ramie type , 1997 .

[18]  J. Sugiyama,et al.  Nanodomains of I a and I Cellulose in Algal Microfibrils , 1998 .

[19]  B. Evans,et al.  Substrate-enzyme interactions in cellulase systems , 1996 .

[20]  S. Ganno,et al.  Sensitive ultraviolet monitoring of aldoses in automated borate complex anion-exchange chromatography with 2-cyanoacetamide. , 1981, Analytical biochemistry.

[21]  A. Hirai,et al.  CP/MAS carbon-13 NMR spectra of the crystalline components of native celluloses , 1987 .

[22]  Hiroyuki Yamamoto,et al.  In situ crystallization of bacterial cellulose II. Influences of different polymeric additives on the formation of celluloses Iα and Iβ at the early stage of incubation , 1996 .