Chain length selectivity during the polycondensation of siloxane-containing esters and alcohols by immobilized Candida antarctica lipase B

Frampton, Mark B.; Zelisko, Paul M.

doi:10.1016/j.enzmictec.2014.03.006

Cited by 7 publications

(31 citation statements)

References 26 publications

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“…To probe the potentialo fr estricted rotation in inhibiting substrate binding, severalv inylsilanes,a sw ell as saturated siloxane-containinga cyl donors and acceptors, were synthesized ( Figure 18). [91] There was ac learp reference by CalB for saturated and trans-unsaturatede sters and alcohols over their cis counterparts. The cis geometry inhibitede ster entry into the active site, or nucleophilic attack of the serine residue.…”

Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

“…[91,106] While examiningt he enzymatic oligomerizationo ft he cyclic siloxanes, Framptone tal. [91] realizedt hat there was very little difference in substratec onversion if the chain lengths weres ufficiently long and, as such, hydrophobic.…”

Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

“…The distance between the methoxy oxygen of the ester to the silicon atom correlates to transesterification of trisiloxane-containing esters. [91] Ester showedt hat the requirement for complete transesterification of all four esters was not an obligate requirement for oligomerization. In fact, dimers andt rimers could be detected, often within the first half hour,d epending on the reacting partners that were used.…”

Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

“…determined that the relative proximity of the TMDS group to the carboxylic acid presented too much stericinterference for the enzyme to function well. [91] In 2010, Poojari and Clarson synthesized silicone aromatic polyesters and polyamides in toluene and under reduced pressure. [90] By using dimethyl terephthalate ande ither a,w-hydroxypropyl-or a,w-aminopropyl-terminated silicones, aromatic polyesters and polyamides were produced, giving aw eightaverage molecular mass of 52 000 gmol À1 for polyesters and 60 000 gmol À1 for polyamides.I ne ither case, the dispersity of the weight-average molecular weights decreased over the course of the 96 hr eaction to reacha sl ow as 1.37 and 1.50, respectively.…”

Section: Polymerizationmentioning

confidence: 99%

“…[103] Dimethyle sponding alcohol was the most preferred of all of the alcohols included in the study. [91] Substrate-enzyme interactions had been proposed to affect catalysis. [105] Framptona nd Zelisko synthesized as eries of trisiloxane esters (Figure 19) to examinet he contribution that the larger bulk of the dimethylsiloxy groups hado nt he overall capacity of the enzyme to carry out catalysis.…”

Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

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Biocatalysis in Silicon Chemistry

Frampton

Zelisko

2017

Chemistry An Asian Journal

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The application of biocatalytic or chemoenzymatic techniquesi ns ilicon chemistry serves two roles:i tp rovides ag reater understanding of the processing of silicon species by natural systems, such as plants, diatoms, and sponges, as well openingu pa venues to green methodologies in the field. In the latter case, biocatalytic approaches have been applied to the synthesis of small-molecule systems and polymeric materials. Often these biocatalytic approaches allow access to molecular structures under mild conditions and, in some cases, molecular structures that are not accessible throught raditional chemical methodologies. Ar eview of recent advances in the applications of biocatalysis in silicon chemistry is presented.

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Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

Section: Polymerizationmentioning

confidence: 99%

Section: Chain-length Selectivity By Calbmentioning

confidence: 99%

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Biocatalysis in Silicon Chemistry

Frampton

Zelisko

2017

Chemistry An Asian Journal

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A short synthesis of siloxane phosphocholines

Frampton

Zelisko

2016

Euro J Lipid Sci & Tech

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Herein, we report our first generation synthesis of two new silicon‐containing phosphocholines (SiPCs) in which the fatty acid chains are terminated by trisiloxane units. We have been exploring the limits to which immobilized lipases can be used in the field of organosilicon chemistry, and the cornerstone of this work is a chemoenzymatic approach to synthesizing SiPCs that are structurally analogous to naturally occurring species such as 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine (POPC). Practical applications: This research focuses on the chemoenzymatic synthesis of siloxane‐containing phospholipid systems. These compounds have different surface properties than the comparable biologically relevant phospholipids opening the doors for the potential application of these siloxane‐containing species as encapsulation/delivery vehicles and as a means of modifying surfaces. Surface pressure‐molecular area isotherms for siloxane‐phospholipids.

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