Toxicological Analysis of the Arylnaphthalene Lignan Justicidin B Using a Model.

The screening of plant-derived compounds with anti-cancer properties is a promising strategy to meet the growing need for new, safe and effective anti-cancer drugs. Justicidin B is a plants secondary metabolite that displays anti-cancer properties in several tumor cells. Therefore, it represents a good candidate.

LCA analysis for assessing environmenstal sustainability of new biobased chemicals by valorising citrus waste.

The global shift towards using biomass for biofuels and chemicals is accelerating due to increasing environmental concerns and geopolitical strategies. This study investigates a biorefinery model using citrus-processing-waste, specifically citrus pulp, to produce high-value products for various industries, including cosmetics, pharmaceuticals, flavours, fragrances, and food packaging. In Italy, particularly Sicily region, citrus processing generates significant amounts of waste, often improperly disposed of, contributing to environmental problems.

Adventitious and Hairy-Roots Cultures as Lignan Plant Factories.

Plants synthesize specific secondary metabolites for survival, reproduction, environmental resilience, and defense. Among them, lignans are a class of polyphenols with several bioactive properties: chemopreventive, anti-inflammatory, antiviral, and antioxidant. These compounds are often extracted from field-grown plants with very low yields.

Optimized Ultrasound-Assisted Extraction of Lignans from Species with Green Solvents.

Lignans are plant phenols derived from phenylpropanoids. They play a significant role in plant defense and have features that make them appealing for pharmaceutical applications. Lignans can be obtained by plant in vitro cultures; their production by adventitious and hairy roots of species seems to be a promising alternative to chemical synthesis.

NMR Characterization of Lignans.

Lignans are particularly interesting secondary metabolites belonging to the phenyl-propanoid biosynthetic pathway. From the structural point of view, these molecules could belong to the aryltetralin, arylnaphtalene, or dibenzylbutyrolactone molecular skeleton. Lignans are present in different tissues of plants but are mainly accumulated in seeds.

Enhanced Aryltetralin Lignans Production in Adventi-Tious Root Cultures.

Lignans are the main secondary metabolites synthetized by species as plant defense molecules. They are also valuable for human health, in particular, for their potent antiviral and antineoplastic properties. In this study, the adventitious root cultures of three species (, and ) were developed to produce aryltetralin lignans.

New Insight into Justicidin B Pathway and Production in .

Lignans are the main secondary metabolites synthetized by species as plant defense compounds but they are also valuable for human health, in particular, for novel therapeutics. In this work, in vitro cultures, cells (Cc), adventitious roots (ARc) and hairy roots (HRc) were developed for the production of justicidin B through elicitation with methyl jasmonate (MeJA) and coronatine (COR). The performances of the cultures were evaluated for their stability, total phenols content and antioxidant ability.

Encapsulated Laccases for the Room-Temperature Oxidation of Aromatics: Towards Synthetic Low-Molecular-Weight Lignins.

A new approach for the encapsulation of laccases with enhanced activity and stability by biomimetic silica mineralisation is reported. A range of lignin model compounds, which includes syringol, syringyl acid, 4-vinylphenol, gallic acid, vanillic acid and guaiacol, was oxidised to lignin-type polymers by the silica-immobilised laccase systems at room temperature. The oxidation rate of the immobilised systems was lower than that of the free enzyme counterparts, but interesting products were observed with the new bio-catalytic materials, which showed reusability and good stability.

Hemp hurds biorefining: A path to green L-(+)-lactic acid production.

Sugars streams generated by organosolv pretreatment of hemp hurds, cellulose (C6) and hemicellulose (C5) fractions, were fermented to lactic acid (LA) by Bacillus coagulans strains XZL4 and DSM1. Pretreatment conditions and enzymatic hydrolysis were optimized and B. coagulans aptness to use lignocellulosic-derived sugars as a carbon source was evaluated.

Fractionation of hemp hurds by organosolv pretreatment and its effect on production of lignin and sugars.

Fractionation of hemp hurds into its three main components, cellulose, hemicellulose, and lignin, was carried out using organosolv pretreatment. The effect of processing parameters, such as temperature, catalyst concentration, reaction time, and methanol (MeOH) concentration, on the dissolution and recovery of hemicellulose and lignin was determined. More than 75% of total hemicellulose and 75% of total lignin was removed in a single step with low amounts of degradation products under the following conditions: 165 °C, 3% H2 SO4 , 20 min reaction time, and 45% MeOH.

The quest for new mild and selective modifications of natural structures: laccase-catalysed oxidation of ergot alkaloids leads to unexpected stereoselective C-4 hydroxylation.

Laccase-catalysed oxidation of ergot alkaloids in the absence of chemical mediators allowed the unexpected isolation of the mono-hydroxylated derivatives of compounds 2-7. Structure determination by NMR techniques clearly indicated that hydroxylation took place at the C-4 benzylic position. Quite notably, the proposed protocol allowed, for the first time, functionalisation at the C-4 position of the ergoline skeleton.

Effects of water miscible organic solvents on the activity and conformation of the Baeyer-Villiger monooxygenases from Thermobifida fusca and Acinetobacter calcoaceticus: a comparative study.

A broader exploitation of enzymes in organic synthesis can be achieved by increasing their tolerance toward organic solvents. In this study, the stability and activity of Baeyer-Villiger monooxygenases from Thermobifida fusca (PAMO) and Acinetobacter sp. (CHMO) in the presence of water miscible organic solvents were compared.

Preparative-scale separation by simulated moving bed chromatography of biocatalytically produced regioisomeric lactones.

The separation of enantiomerically pure, but regioisomeric compounds by chromatography is attractive for the production of chiral compounds, if the process leads to high-purity products in high yield with excellent throughput and reduced solvent use. The biocatalytic Baeyer-Villiger oxidation of racemic ketones gives rapid access to an equimolar mixture of regioisomeric lactones with excellent enantiomeric purity. The existing separation methods have so far represented a bottleneck for preparative applications of this technology.

Novel mutants of the human beta1-adrenergic receptor reveal amino acids relevant for receptor activation.

Activation of G protein-coupled receptors like the beta(1)-adrenergic receptor results in conformational changes that ultimately lead to signal propagation through a G protein to an effector like adenylyl cyclase. In this study we identified amino acids that seem to be critical for activation of the human beta(1)-adrenergic receptor. Activation patterns of mutant receptors were analyzed using two structurally different ligands for beta-adrenergic receptors that both are mixed agonist/antagonists.

A folding inhibitor of the HIV-1 protease.

Because the human immunodeficiency virus type 1 protease (HIV-1-PR) is an essential enzyme in the viral life cycle, its inhibition can control AIDS. The folding of single-domain proteins, like each of the monomers forming the HIV-1-PR homodimer, is controlled by local elementary structures (LES, folding units stabilized by strongly interacting, highly conserved, as a rule hydrophobic, amino acids). These LES have evolved over myriad generations to recognize and strongly attract each other, so as to make the protein fold fast and be stable in its native conformation.

Polyamino acids as synthetic enzymes: mechanism, applications and relevance to prebiotic catalysis.

Polyamino acids, such as polyleucine, behave as synthetic enzymes in the asymmetric epoxidation of chalcone and other electron-deficient alkenes (the Julià-Colonna reaction). The influences of reaction conditions, of the molecular structure of the catalysts and of the scaling-up of the process on the enantioselectivity of the reaction have been determined. The kinetics and mechanism have been investigated using a soluble PEG-polyleucine conjugate, which behaves in a similar way to an enzyme, showing saturation kinetics for both chalcone and HOO-.

[Cp*Rh(bpy)(H2O)]2+ as a coenzyme substitute in enzymatic oxidations catalyzed by Baeyer-Villiger monooxygenases.

[Cp*Rh(bpy)(H2O)]2+ was applied as a flavin regenerating reagent in BVMO catalyzed oxidations of organic sulfides to chiral sulfoxides.

Kinetics of chalcone oxidation by peroxide anion catalysed by poly-l-leucine.

An insight into the kinetics, mechanism and optimum reaction conditions of the Julia-Colonna epoxidation has been gained using a soluble polyleucine catalyst.

Ab initio study of oxygen atom transfer from hydrogen peroxide to trimethylamine.

Unlike what has been theoretically proposed for ammonia oxidation with hydrogen peroxide, trimethylamine oxidation occurs with a concerted mechanism, which is favored even when an explicit water molecule is added or continuum solvent (water) is simulated.

Modification of the enantioselectivity of two homologous thermophilic carboxylesterases from Alicyclobacillus acidocaldarius and Archaeoglobus fulgidus by random mutagenesis and screening.

The esterase genes est2 from Alicyclobacillus acidocaldarius and AF1716 from Archaeoglobus fulgidus were subjected to error-prone PCR in an effort to increase the low enantioselectivity of the corresponding enzymes EST2 and AFEST, respectively. The model substrate ( RS)- p-nitrophenyl-2-chloropropionate was chosen to produce ( S)-2-chloropropionic acid, an important intermediate in the synthesis of some optically pure compounds, such as the herbicide mecoprop. In the case of EST2, a single mutant, Leu212Pro, was obtained showing a slightly enhanced preference toward the ( S) substrate; in the case of AFEST, a double mutant, Leu101Ile/Asp117Gly, was obtained showing an increased preference in the opposite direction.

Subtilisin-catalyzed esterification of di- and oligosaccharides containing a D-fructose moiety.

Several di- and oligosaccharides containing a D-fructose moiety have been acylated by protease subtilisin in anhydrous dimethylformamide in the presence of the activated ester trifluoroethyl butanoate. Under the reaction conditions used, all the substrates were converted into the corresponding monobutanoates in ca. 50% isolated yields.

Overexpression and properties of a new thermophilic and thermostable esterase from Bacillus acidocaldarius with sequence similarity to hormone-sensitive lipase subfamily.

We previously purified a new esterase from the thermoacidophilic eubacterium Bacillus acidocaldarius whose N-terminal sequence corresponds to an open reading frame (ORF3) reported to show homology with the mammalian hormone-sensitive lipase (HSL)-like group of the esterase/lipase family. To compare the biochemical properties of this thermophilic enzyme with those of the homologous mesophilic and psychrophilic members of the HSL group, an overexpression system in Escherichia coli was established. The protein, expressed in soluble and active form at 10 mg/l E.

Coenzymatic properties of low molecular-weight and macromolecular N6-derivatives of NAD+ and NADP+ with dehydrogenases of interest for organic synthesis.

The catalytic activity, expressed as Km and Vmax values, of 16 enzymes of practical interest with the macromolecular coenzymes poly(ethylene glycol)-N6-(2-aminoethyl)-NAD+ and poly(ethylene glycol)-N6-(2-aminoethyl)-NADP+ and their low molecular weight precursors N6-(2-aminoethyl)-NAD+ and N6-(2-aminoethyl)-NADP+, was investigated. The enzymes examined are of direct interest for organic synthesis (i.e.