Post translational modifications of Trifolitoxin: a blue fluorescent peptide antibiotic*

Trifolitoxin (TFX, C41H63N15O15S) is a selective, ribosomally-synthesized, post-translationally modified, peptide antibiotic, produced by Rhizobium leguminosarum bv. trifolii T24. TFX specifically inhibits α-proteobacteria, including the plant symbiont Rhizobium spp., the plant pathogen Agrobacterium spp. and the animal pathogen Brucella abortus. TFX-producing strains prevent legume root nodulation by TFX-sensitive rhizobia. TFX has been isolated as a pair of geometric isomers, TFX1 and TFX2, which are derived from the biologically inactive primary amino acid sequence: Asp-Ile-Gly-Gly-Ser-Arg-Gln-Gly-Cys-Val-Ala. Gly-Cys is present as a thiazoline ring and the Arg-Gln-Gly sequence is extensively modified to a UV absorbing, blue fluorescent chromophore. The chromophore consists of a conjugated, 5-membered heterocyclic ring and side chain of modified glutamine.

Extraction of Essential oils from Cymbopogon citratus using Organic solvents

Essential oils are extracted from diverse plants and used in medicinal field for diverse conditions. The presence of unique aromatic compounds imparts aroma and medicinal values. Essential oil plays a vital role in pharmaceutical, cosmetics and also acts as rejuvenate. Though there are various plants from which essential oil are extracted, our study focuses on the extraction and comparison of the phytochemicals released from the fresh leaves of Cymbopogon citratus using two different organic solvents; (a). hexane (b) hexane and toluene in the ratio 1:1. Extraction was performed for 16 hours in Soxhlet extractor. The amount of oil obtained was weighed in both extractions and subjected to GC MS for phytochemical analysis. Results revealed that when the solvents hexane and toluene in the ratio 1:1 was used it gave a better yield of 3% from 5 gram of fresh leaves, while hexane yielded only 1.5%. The GC-MS analysis revealed that the compound released from both extractions are of diverse medicinal values and can be used in aromatherapy as rejuvenate. The compounds nerol (2,6 octadienal, 3,7 dimethyl.Z) and geraniol (2,6 octadienal, 3,7 dimethyl) are the common phytochemicals extracted .Nerol and geraniol are geometric isomers. Geraniol is reported as an efficient anticancer agent with additional properties of analgesic, antinflammatory and antiseptic values. Nerol is used as a fragrance. The compound 1 acetyl 4 hydroxy pyrrolidine 2 one is extracted when hexane and toluene were used for extraction in the ratio 1:1. It is reported to be anti-rheumatic and effective in the treatment of hips and joints. Hence it can be concluded that hexane and toluene in the ratio 1:1 can be used for extraction of oil considering its medicinal values and the increased % of extraction rather than using hexane alone.

Biological Inspirations: Iron Complexes Mimicking the Catechol Dioxygenases

Within the broad group of Fe non-heme oxidases, our attention was focused on the catechol 1,2- and 2,3-dioxygenases, which catalyze the oxidative cleavage of aromatic rings. A large group of Fe complexes with N/O ligands, ranging from N3 to N2O2S, was developed to mimic the activity of these enzymes. The Fe complexes discussed in this work can mimic the intradiol/extradiol catechol dioxygenase reaction mechanism. Electronic effects of the substituents in the ligand affect the Lewis acidity of the Fe center, increasing the ability to activate dioxygen and enhancing the catalytic activity of the discussed biomimetic complexes. The ligand architecture, the geometric isomers of the complexes, and the substituent steric effects significantly affect the ability to bind the substrate in a monodentate and bidentate manner. The substrate binding mode determines the preferred mechanism and, consequently, the main conversion products. The preferred mechanism of action can also be affected by the solvents and their ability to form the stable complexes with the Fe center. The electrostatic interactions of micellar media, similar to SDS, also control the intradiol/extradiol mechanisms of the catechol conversion by discussed biomimetics.

DFT Calculations of 1H NMR Chemical Shifts of Geometric Isomers of Conjugated Linolenic Acids, Hexadecatrienyl Pheromones, and Model Triene-Containing Compounds: Structures in Solution and Revision of NMR Assignments

A DFT study of the 1H NMR chemical shifts, δ(1H), of geometric isomers of 18:3 conjugated linolenic acids (CLnAs), hexadecatrienyl pheromones, and model triene-containing compounds is presented, using standard functionals (B3LYP and PBE0) as well as corrections for dispersion interactions (B3LYP-D3, APFD, M06–2X and ωB97XD). The results are compared with literature experimental δ(1H) data in solution. The closely spaced “inside” olefinic protons are significantly more deshielded due to short-range through-space H…H steric interactions and appear close to or even beyond δ-values of aromatic systems. Several regularities of the computational δ(1H) of the olefinic protons of the conjugated double bonds are reproduced very accurately for the lowest-energy DFT-optimized single conformer for all functionals used and are in very good agreement with experimental δ(1H) in solution. Examples are provided of literature studies in which experimental resonance assignments deviate significantly from DFT predictions and, thus, should be revised. We conclude that DFT calculations of 1H chemical shifts of trienyl compounds are powerful tools (i) for the accurate prediction of δ(1H) even with less demanding functionals and basis sets; (ii) for the unequivocal identification of geometric isomerism of conjugated trienyl systems that occur in nature; (iii) for tackling complex problems of experimental resonance assignments due to extensive signal overlap; and (iv) for structure elucidation in solution.

Adonis amurensis Is a Promising Alternative to Haematococcus as a Resource for Natural Esterified (3S,3′S)-Astaxanthin Production

Astaxanthin (AST) characteristics and pigment productivity of Adonis amurensis, one of the few AST-producing higher plants, have not yet been studied extensively. In this study, the geometrical and optical isomers of AST in different parts of the A. amurensis flower were determined in detail, followed by a separation of the all-trans AST using HPLC chromatography. AST extracted from the flower accounted for 1.31% of the dry weight (dw) and mainly existed in the di-esterified form (>86.5%). The highest concentration was found in the upper red part of the petal (3.31% dw). One optical isomer (3S, 3′S) of AST, with five geometrical isomers (all-trans, 9-cis, 13-cis, 15-cis, and di-cis) were observed in all parts of the flower. All-trans AST was the predominant geometrical isomer accounting for 72.5% of the total content of geometric isomers in total flower, followed by the 13-cis, and 9-cis isomers. The all-trans AST isomer was also isolated, and then purified by HPLC from the crude oily flower extract, with a 21.5% recovery yield. The cis-AST extracted from the combined androecium and gynoecium gives a very strong absorption in the UVA region due to a high level of cis, especially di-cis, isomers, suggesting a prospective use in the preparation of anti-ultraviolet agents. The production cost of AST from Adonis flowers can be as low as €388–393/kg. These observations together with other factors such as the low technology requirement for plant culturing and harvesting suggest Adonis has great potential as a resource for natural esterified (3S,3′S)-AST production when compared with Haematococcus culturing.