A unique nanoporous sol-gel glass possessing a highly ordered porous structure (with a pore size of 153 A in diameter) was examined for use as a support material for enzyme immobilization. A model enzyme, alpha-chymotrypsin, was efficiently bound onto the glass via a bifunctional ligand, trimethoxysilylpropanal, with an active enzyme loading of 0.54 wt%. The glass-bound chymotrypsin exhibited greatly enhanced stability both in aqueous solution and organic solvents. The half-life of the glass-bound alpha-chymotrypsin was >1000-fold higher than that of the native enzyme, as measured either in aqueous buffer or anhydrous methanol. The enhanced stability in methanol, which excludes the possibility of enzyme autolysis, particularly reflected that the covalent binding provides effective protection against enzyme inactivation caused by structural denaturation. In addition, the activity of the immobilized alpha-chymotrypsin was also much higher than that of the native enzyme in various organic solvents. From these results, it appears that the glass-enzyme complex developed in the present work can be used as a high-performance biocatalyst for various chemical processing applications, particularly in organic media. Published by John Wiley & Sons
Aminodimethylalanes
R1R2NAlMe2 (R1 =
2,6-i-Pr2C6H3,
2,6-Me2C6H3; R2 =
SiMe3, Si(i-Pr)Me2, Si(t-Bu)Me2,
Si(2,4,6-Me3C6H2)Me2)
are prepared in high yield via reaction of the
respective amine R1R2NH with
trimethylaluminum in n-hexane. Further reaction of
(2,6-i-Pr2C6H3)N(SiMe3)AlMe2
with 2 equiv of trimethyltin fluoride in toluene affords
the
aminoalane difluoride
(2,6-i-Pr2C6H3)N(SiMe3)AlF2.
An X-ray structural determination of
(2,6-i-Pr2C6H3)N(SiMe3)AlMe2
shows it to be dimeric with bridging methyl and terminal
amino groups. The aminoalane difluoride
(2,6-i-Pr2C6H3)N(SiMe3)AlF2
is trimeric with a
six-membered alternating aluminum−fluorine ring. Terminal
fluorine atoms are located
above and below the ring. Reactions of aminoalanes
R1R2NAlMe2 with 2 equiv of
trimethyltin
fluoride in THF yield the monomeric THF adducts
R1R2NAlF2·THF.
Weak arene–thallium interactions and T1T1 contacts stabilize the molecular framework of the tetrameric title compound in the solid state. The picture on the right shows two monomeric units and the central T14 ring. The first covalent TlI compound can be prepared easily from LiN(SiMe3)(2,6‐iPr2C6H3) and T1C1 in n‐hexane.
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