Environmental comparison of biobased chemicals from glutamic acid with their petrochemical equivalents.

Glutamic acid is an important constituent of waste streams from biofuels production. It is an interesting starting material for the synthesis of biobased chemicals, thereby decreasing the dependency on fossil fuels. The objective of this paper was to compare the environmental impact of four biobased chemicals from glutamic acid with their petrochemical equivalents, that is, N-methylpyrrolidone (NMP), N-vinylpyrrolidone (NVP), acrylonitrile (ACN), and succinonitrile (SCN). A consequential life cycle assessment was performed, wherein glutamic acid was obtained from sugar beet vinasse. The removed glutamic acid was substituted with cane molasses and ureum. The comparison between the four biobased and petrochemical products showed that for NMP and NVP the biobased version had less impact on the environment, while for ACN and SCN the petrochemical version had less impact on the environment. For the latter two an optimized scenario was computed, which showed that the process for SCN can be improved to a level at which it can compete with the petrochemical process. For biobased ACN large improvements are required to make it competitive with its petrochemical equivalent. The results of this LCA and the research preceding it also show that glutamic acid can be a building block for a variety of molecules that are currently produced from petrochemical resources. Currently, most methods to produce biobased products are biotechnological processes based on sugar, but this paper demonstrates that the use of amino acids from low-value byproducts can certainly be a method as well.

Synthesis of biobased succinonitrile from glutamic acid and glutamine.

Succinonitrile is the precursor of 1,4-diaminobutane, which is used for the industrial production of polyamides. This paper describes the synthesis of biobased succinonitrile from glutamic acid and glutamine, amino acids that are abundantly present in many plant proteins. Synthesis of the intermediate 3-cyanopropanoic amide was achieved from glutamic acid 5-methyl ester in an 86 mol% yield and from glutamine in a 56 mol % yield. 3-Cyanopropanoic acid can be converted into succinonitrile, with a selectivity close to 100% and a 62% conversion, by making use of a palladium(II)-catalyzed equilibrium reaction with acetonitrile. Thus, a new route to produce biobased 1,4-diaminobutane has been discovered.

Mutation of His465 alters the pH-dependent spectroscopic properties of Escherichia coli glutamate decarboxylase and broadens the range of its activity toward more alkaline pH.

Glutamate decarboxylase (GadB) from Escherichia coli is a hexameric, pyridoxal 5'-phosphate-dependent enzyme catalyzing CO(2) release from the alpha-carboxyl group of L-glutamate to yield gamma-aminobutyrate. GadB exhibits an acidic pH optimum and undergoes a spectroscopically detectable and strongly cooperative pH-dependent conformational change involving at least six protons. Crystallographic studies showed that at mildly alkaline pH GadB is inactive because all active sites are locked by the C termini and that the 340 nm absorbance is an aldamine formed by the pyridoxal 5'-phosphate-Lys(276) Schiff base with the distal nitrogen of His(465), the penultimate residue in the GadB sequence. Herein we show that His(465) has a massive influence on the equilibrium between active and inactive forms, the former being favored when this residue is absent. His(465) contributes with n approximately 2.5 to the overall cooperativity of the system. The residual cooperativity (n approximately 3) is associated with the conformational changes still occurring at the N-terminal ends regardless of the mutation. His(465), dispensable for the cooperativity that affects enzyme activity, is essential to include the conformational change of the N termini into the cooperativity of the whole system. In the absence of His(465), a 330-nm absorbing species appears, with fluorescence emission spectra more complex than model compounds and consisting of two maxima at 390 and 510 nm. Because His(465) mutants are active at pH well above 5.7, they appear to be suitable for biotechnological applications.