Phosphoryl and Sulfuryl Transfer☆

Brandão, Tiago A. S.; Hengge, Alvan C.

doi:10.1016/b978-0-12-409547-2.12795-7

Cited by 1 publication

(1 citation statement)

References 312 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Overall, many questions still remain about the catalytic mechanism, mainly regarding the role of acid–base chemistry on silica materials. In this work, we give new evidence that general acid–base catalysis plays a key role in the hydrolysis of phosphate esters by amorphous silica materials, which, like enzymatic reactions, represents the most frequent pathway for catalysis of hydrolytic reactions. − …”

Section: Introductionmentioning

confidence: 95%

Efficient Catalysis of Phosphate Ester Hydrolysis by Bare Silica

et al. 2020

View full text Add to dashboard Cite

This work reports the catalysis of bare silica materials (MCM-41, SBA-15, and silica gel) for the complete hydrolyses of bis(2,4-nitrophenyl)phosphate (BDNPP) and bis(4nitrophenyl)phosphate (BNPP), which share the same phosphate diester chemical core with important biological molecules, DNA and RNA, and toxic substances like EA2192 and anatoxin-a(s). Catalytic effects above 7000-fold were observed for the hydrolysis of BNPP, which were consistent with a concerted S N 2(P) mechanism under the action of siloxide and silanol groups that provide water activation by general base catalysis and leavinggroup departure stabilization by general acid catalysis, respectively. We also observed that product formation follows a sigmoidal behavior as a result of catalytic effect enhancement following an induction period. This effect is discussed considering cooperative effects caused by silica hydration, which is unchanged upon material reuse affording strong catalytic effects for phosphate diester hydrolyses and no induction periods.

show abstract

Section: Introductionmentioning

confidence: 95%