Fatty
acid diesters of 2,5-bis-(hydroxymethyl)furan (BHMF), promising candidates
as sustainable bioadditives for increasing the cetane number of biodiesel
fuels, were prepared through a solvent-free Novozym 435-mediated diesterification
of BHMF with a fatty acid mixture (FAM) resulting from the hydrolysis
of commercial sunflower oil. Under solvent-free conditions and a 15
mbar vacuum, high conversions into diesters were obtained in the heterogeneous
reaction, after the gradual solubilization of BHMF. After optimization
studies (temperature, reaction time, BHMF–FAM ratio, and biocatalyst
loading), more than 97% conversion into diesters was achieved. The
calculated sustainability metrics support the fact that the currently
described solvent-free method represents an improved synthetic procedure
for the preparation of BHMF fatty acid diesters.
We report a simple enzymatic procedure
for the synthesis of short-chained
flavor esters by direct esterification of natural acids with short-chain
primary alcohols mediated by lipase B from Candida
antarctica entrapped in a tailored sol–gel
matrix in the presence of three additives, using vacuum for water
removal. Maximal immobilization yields (100%) were obtained for all
three biocatalysts, while the enzyme loading and the synthetic activity
depend on the used additive (6.7, 7.6, and 7.7 μg enzyme/mg
biocatalyst for β-cyclodextrin, polyvinyl alcohol, and glycerol,
respectively, and 76–110% recovered activity as compared with
free lipase). The process was optimized using the reaction of hexan-1-ol
with butyric acid as the model with significant conversion improvements
(from <40% to >94%) reducing the alcohol/enzyme ratio (from
100:1
to 25:1 weight ratio) for all novel biocatalysts. Other short-chain
flavor esters were prepared with excellent yields (>90%) under
the
previously established optimal conditions. Atom economy (90.53), E-factor (17.22), atom efficiency (88.36), mass intensity
(18.58), and reaction mass efficiency (60.07) as relevant sustainability
metrics were calculated for the preparative scale model reaction with
glycerol as the additive. Based on our results, this green and sustainable
new approach can be used for the synthesis of many flavor esters.
The enzymes encapsulation in sol-gel matrix can be improved using some additive acting on enzyme activity and/or stability. Ionic liquids, poly-hydroxy compounds, sugars, etc. have been previously reported as additives....
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