A Combined Bio-Chemical Synthesis Route for 1-Octene Sheds Light on Rhamnolipid Structure

Abstract

Here we report a chemoenzymatic approach to synthesize 1-octene from carbohydrates via ethenolysis of rhamnolipids. Rhamnolipids synthesized by P. putida contain a double bond between carbon five and six, which is experimentally confirmed via olefin cross metathesis. Utilizing these lipids in the ethenolysis catalyzed by a Grubbs−Hoveyda-type catalyst selectively generates 1-octene and with good conversions. This study shows the potential of chemoenzymatic approaches to produce compounds for the chemical industry from renewable resources.

Key Chemical Kinetic Steps in Reaction Mechanisms for Fuels from Biomass: A Perspective

“…Examples of such fuels from biomass are 1-octene 1 and n-octanol, 3 both produced from biomass, as discussed by Leitner et al 2 as some of the hydrocarbon fuels from the RWTH program "Tailor-made fuels from biomass" 34 and its successor "The Fuel Science Center". 35 These are fuels which that have initial combustion structures, such as linear arrays of (CH 2 ) groups, of fuels that immediately are subject to cool flame chemistry.…”

“…Many biodiesel fuel molecules, to be discussed in detail below, contain at least one CC double bond that determines many of the important combustion characteristic of biodiesel fuels, and virtually all hydrocarbon and related kinetic models must include the reaction and structural features that are best illustrated in olefin fuel kinetic mechanisms. Tiso et al 1 recently developed another biochemical process to convert biomass to industrially relevant intermediates for subsequent chemical conversion to 1-octene. This process starts with a soil bacterium that is treated to produce a specific carbohydrate that has a CC double bond at a predictable site in the molecule, and that carbohydrate is then treated with a chemoenzymatic approach to synthesize 1-octene with predictable specificity.…”

“…There are several ways in which low-temperature reactions and cool flame kinetics may be important for present and future fuels from biomass. Some of the fuels that are currently being produced from biomass are rather conventional hydrocarbon and related fuels that experience the full range of low-temperature kinetics and will be discussed below. Examples of such fuels from biomass are 1-octene and n -octanol, both produced from biomass, as discussed by Leitner et al as some of the hydrocarbon fuels from the RWTH program “Tailor-made fuels from biomass” and its successor “The Fuel Science Center” . These are fuels which that have initial combustion structures, such as linear arrays of (CH 2 ) groups, of fuels that immediately are subject to cool flame chemistry. Future fuels from biomass may contain sites where abstraction of H atoms or other radicals provide an equilibrium similar to that which R–O 2 exhibits for hydrocarbon fuels.…”

“…Progress is being made in producing familiar, industrially useful molecules from microbial fermentations from biomass , in new programs that are emphasizing the synthesis of “old” chemicals from biomass. This approach can be understood as employing an ingenious way to recycle CO 2 by treating biomass as the source of the useful carbon in the form of molecules such as 1-octene or 1-octanol, rather than collecting it directly out of the atmosphere, thereby using microbial plants to do the work of putting the carbon into a usable form.…”

Impact of the number of rhamnose moieties of rhamnolipids on the structure, lateral organization and morphology of model biomembranes

“…a-L-Rhamnopyranosyl-b-hydroxydecanoyl-b-hydroxy-decanoate (RhaC 10 C 10 ), 2-O-a-L-rhamnopyra-nosyl-a-L-rhamnopyranosyl-bhydroxydecanoyl-b-hydroxydecanoate (RhaRhaC 10 C 10 ) and 3-(3hydroxydecanoyloxy)decanoate (HAA) were obtained, characterized and purified by a combination of an adsorption/desorption and preparative liquid chromatography as described before. 7,39 Briefly, after protein precipitation, the supernatant was adsorbed using the silica adsorbent AA12SA5 (YMC Europe GmbH Dinslaken, Germany). Subsequently, desorption was carried out with ethanol.…”