Lignin is a major component of lignocellulosic biomass and as such, it is processed in enormous amounts in the pulp and paper industry worldwide. In such industry it mainly serves the purpose of a fuel to provide process steam and electricity, and to a minor extent to provide low grade heat for external purposes. Also from other biorefinery concepts, including 2nd generation ethanol, increasing amounts of lignin will be generated. Other uses for lignin - apart from fuel production - are of increasing interest not least in these new biorefinery concepts. These new uses can broadly be divided into application of the polymer as such, native or modified, or the use of lignin as a feedstock for the production of chemicals. The present review focuses on the latter and in particular the advances in the biological routes for chemicals production from lignin. Such a biological route will likely involve an initial depolymerization, which is followed by biological conversion of the obtained smaller lignin fragments. The conversion can be either a short catalytic conversion into desired chemicals, or a longer metabolic conversion. In this review, we give a brief summary of sources of lignin, methods of depolymerization, biological pathways for conversion of the lignin monomers and the analytical tools necessary for characterizing and evaluating key lignin attributes.
The conversion of lignin to potentially high-value low molecular weight compounds often results in complex mixtures of monomeric and oligomeric compounds. In this study, a method for the quantitative and qualitative analysis of 40 lignin-derived compounds using ultra-high-performance supercritical fluid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UHPSFC/QTOF-MS) has been developed. Seven different columns were explored for maximum selectivity. Makeup solvent composition and ion source settings were optimised using a D-optimal design of experiment (DoE). Differently processed lignin samples were analysed and used for the method validation. The new UHPSFC/QTOF-MS method showed good separation of the 40 compounds within only 6-min retention time, and out of these, 36 showed high ionisation efficiency in negative electrospray ionisation mode.
Graphical abstractA rapid and selective method for the quantitative and qualitative analysis of 40 lignin-derived compounds using ultra-high-performance supercritical fluid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UHPSFC/QTOF-MS)
Electronic supplementary materialThe online version of this article (10.1007/s00216-017-0663-5) contains supplementary material, which is available to authorized users.
The profiles of carotenoids and production of β-carotene by six eustigmatophytes, Eustigmatos magnus, Eustigmatos polyphem, Eustigmatos vischeri, Vischeria helvetica, Vischeria punctata and Vischeria stellata, grown in a bubble column photobioreactor were measured. All eustigmatophytes contained β-carotene, violaxanthin and vaucheriaxanthin as their major carotenoids and accumulated large amount of β-carotene, which accounted for over 50 % of total carotenoids. Maximum intracellular β-carotene contents ranged 1.5-3.5 % of dry wt and in V. stellata it reached 5.9 % dry wt, accompanied by a biomass dry wt >7.3 g/l, with the highest up to 9.8 g/l. These eustigmatophytes are thus promising producers of β-carotene.
Gymnemic acid (GA) isolated from Gymnema
sylvestre (Retz.) Schult. has been shown
to have antihyperglycemic activity; however, the molecular mechanisms
governing these effects are unclear. In this study, GA (40 and 80
mg kg–1 day–1) was evaluated by
type 2 diabetes mellitus (T2DM) rats to explore its hypoglycemic activity
and underlying mechanisms of action. The results indicated that GA
decreased fasting blood glucose (FBG) concentrations by 26.7% and
lowered insulin concentrations by 16.1% after oral administration
of GA at a dose of 80 mg kg–1 day–1 for 6 weeks in T2DM rats. Our data showed that real-time polymerase
chain reaction and western blot indicated that GA upregulated the
level of phosphatidylinositol-3-kinase (PI3K) and glycogen synthesis
(GS) and promoted the phosphorylation of protein kinase B (Akt) while
downregulated the expression of glycogen synthesis kinase-3β
(GSK-3β) in T2DM rats. In addition, key proteins involved in
adenosine monophosphate (AMP)-activated protein kinase (AMPK)-mediated
gluconeogenesis [such as phosphoenolpyruvate carboxy kinase (PEPCK)
and glucose-6-phosphatase (G6Pase)] were downregulated in GA-treated
T2DM rats. In summary, the hypoglycemic mechanisms of GA may be related
to promoting insulin signal transduction and activating PI3K/Akt-
and AMPK-mediated signaling pathways in T2DM rats.
Gymnemic acid (GA) is an herbal ingredient that can improve glucose metabolism in patients with diabetes mellitus. In this study, we evaluated the ameliorative effects of GA on insulin resistance (IR) and identified the mechanisms in type 2 diabetes mellitus (T2DM) rats and IR HepG2 cells. GA effectively enhanced glucose uptake in IR HepG2 cells from 11.9 ± 1.09 to 14.7 ± 1.38 mmol/L and lowered fasting blood glucose (blood glucose levels in groups treated with GA at 40 and 80 mg/kg/day were reduced by 15.2% and 26.7%, respectively) and oral glucose tolerance. Both in vivo and in vitro, GA downregulated the expression of endoplasmic reticulum (ER) stress indicator proteins such as ORP150, p-c-Jun, p-PERK, and p-eIF2α. In addition, the improvement of ER stress regulated the insulin signal transduction proteins, reducing p-IRS-1(ser) levels and increasing p-IRS-1(tyr) in GA-treated T2DM rats and IR HepG2 cells. In summary, the mechanism underlying the hypoglycemic effects of GA may be associated with alleviation of ER stress and facilitation of insulin signal transduction in T2DM rats and IR HepG2 cells.
Lignin depolymerisation produces a large variety of low molecular weight phenolic compounds that can be upgraded to value-added chemicals. Detailed analysis of these complex depolymerisation mixtures is, however, hampered by the lack of resolving power of traditional analysis techniques. In this study, a novel online comprehensive two-dimensional reversed-phase liquid chromatography (RPLC) × supercritical fluid chromatography (SFC) method with trapping column interface was developed for the separation of phenolic compounds in depolymerised lignin samples. The trapping capacities of different trapping columns were evaluated. The influence of large volume water-containing injection on SFC performance was studied. The relation between peak capacity and first dimension flow rate and gradient was investigated. The optimized method was applied for the analysis of a depolymerised lignin sample. The RPLC × SFC system exhibited high degree of orthogonality. Compared with traditional loop based interface, trapping column interface can significantly shorten the analysis time and offer higher detectability, with the disadvantage of more severe undersampling in the first dimension.
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