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1.
J Am Chem Soc ; 146(12): 7963-7970, 2024 Mar 27.
Article En | MEDLINE | ID: mdl-38483110

Cellulose serves as a sustainable biomaterial for a wide range of applications in biotechnology and materials science. While chemical and enzymatic glycan assembly methods have been developed to access modest quantities of synthetic cellulose for structure-property studies, chemical polymerization strategies for scalable and well-controlled syntheses of cellulose remain underdeveloped. Here, we report the synthesis of precision cellulose via living cationic ring-opening polymerization (CROP) of glucose 1,2,4-orthopivalates. In the presence of dibutyl phosphate as an initiator and triflic acid as a catalyst, precision cellulose with well-controlled molecular weights, defined chain-end groups, and excellent regio- and stereospecificity was readily prepared. We further demonstrated the utility of this method through the synthesis of precision native d-cellulose and rare precision l-cellulose.


Cellulose , Glucose , Cellulose/chemistry , Polymerization , Glucose/chemistry , Polysaccharides , Cations
2.
Article En | MEDLINE | ID: mdl-25863453

The crystallization and structure features of xBaO·(90-x)(60P2O5-40Fe2O3)·10CaF2 glasses, where x=0, 5, 10, 15 and 20 mol%, are investigated in details by using X-ray diffraction analysis, Fourier transform infrared spectroscopy, Raman spectroscopy and differential thermal analysis. It is found that the major crystalline phase of barium iron phosphate glasses annealed between 650 °C and 850 °C is FePO4, and the crystallization is restrained by barium. The predominant infrared absorption band is attributed to the antisymmetric stretching vibrations of (PO3)(2-) in Q(1) units. Raman and Fourier transform infrared spectra reveal that the glasses' main structural networks are Q(1) and Q(0) tetrahedrons connected by P-O-P linkages. Moreover, the glass transition temperature increases with BaO content, which suggests that barium can strengthen the thermal stability of the iron phosphate glass.

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