Agnieszka Ludwiczuk

Phytochemical and biological studies of bryophytes.

The bryophytes contain the Marchantiophyta (liverworts), Bryophyta (mosses) and Anthocerotophyta (hornworts). Of these, the Marchantiophyta have a cellular oil body which produce a number of mono-, sesqui- and di-terpenoids, aromatic compounds like bibenzyl, bis-bibenzyls and acetogenins. Most sesqui- and di-terpenoids obtained from liverworts are enantiomers of those found in higher plants. Many of these compounds display a characteristic odor, and can have interesting biological activities. These include: allergenic contact dermatitis, antimicrobial, antifungal and antiviral, cytotoxic, insecticidal, insect antifeedant, superoxide anion radical release, 5-lipoxygenase, calmodulin, hyaluronidase, cyclooxygenase, DNA polymerase β, and α-glucosidase and NO production inhibitory, antioxidant, piscicidal, neurotrophic and muscle relaxing activities among others. Each liverwort biosynthesizes unique components, which are valuable for their chemotaxonomic classification. Typical chemical structures and biological activity of the selected liverwort constituents as well as the hemi- and total synthesis of some biologically active compounds are summarized.

Isolation of terpenoids from Pimpinella anisum essential oil by high‐performance counter‐current chromatography

High-performance counter-current chromatography was successfully used for the isolation and purification of terpenoid compounds from the essential oil of Pimpinella anisum L. A two-phase solvent system composed of n-heptane/methanol/ethyl acetate/water (5:2:5:2, v/v/v/v) was suitable for the purification of linalool, terpinen-4-ol, α-terpineol, p-anisaldehyde, while n-heptane/methanol (1:1, v/v) was used for the isolation of anethole and foeniculin. A scale-up process from analytical to preparative was developed. Additionally, a stepwise gradient elution was applied and instead of two different runs, 40 min each, one 80 min separation was performed; although the time of separation remains the same, it was possible to repeat the efficiency even if the water-containing mobile phase was changed to a nonaqueous system. The obtained essential oil, as well as purified compounds, was analyzed by GC. A total of 0.64 mg of linalool, 0.52 mg of terpinen-4-ol, 0.10 mg of α-terpineol, 0.62 mg of p-anisaldehyde, 15 mg of anethole, and 2.12 mg of foeniculin were obtained from 210 mg of the essential oil of P. anisum L. in a short time with purities of 99, 98, 94, 93.54, 93, and 93.6%, respectively.

Chapter Five: Distribution of Terpenoids and Aromatic Compounds in Selected Southern Hemispheric Liverworts

Abstract Bryophytes contain a large number of terpenoids and aromatic compounds. In this article, the chemical constituents of selected liverworts collected in New Zealand, Malaysia, Madagascar, Argentina, Ecuador, and other southern hemispheric countries are discussed. The southern hemisphere is a region of extraordinarily high liverwort diversity. Many of compounds isolated from these liverworts have been represented by novel carbon skeletons and are important chemical markers of a liverworts genus or family. Many of these compounds also have interesting biological activity.

Separation of the ginsenosides fraction obtained from the roots of Panax quinquefolium L. cultivated in Poland

The objective of the work described in this paper was to investigate the separation of ginsenosides by TLC, HPTLC, and OPLC. The best separation of the ginsenosides was obtained by use of OPLC on silica gel 60F254 with chloroform—methanol—ethyl acetate—water—hexane, 20 + 22 + 60 + 8 + 4 (v/v), as mobile phase. Results from TLC, HPTLC, and OPLC analysis of ginsenosides indicated that use of the different methods of development resulted in significant differences between the resolution of the compounds. Forced-flow OPLC is the most sensitive method for analysis of the ginsenosides.

Phenolic compounds in the flowers of Lavatera trimestris L. (Malvaceae)

Plants of the Malvaceae family are very rich in phenolic compounds. TLC, 2D TLC, and RP HPLC have been used for qualitative analysis of phenolic acids and flavonoids in the flowers of Lavatera trimestris L. Four aglycones, seven glycosides and eleven phenolic acids were identified in the plant, most for the first time. Quantitative analysis of phenolic compounds was also performed.

Identification of cryptic species within liverwort Conocephalum conicum based on the volatile components.

Cryptic speciation refers to cases where species are clearly genetically differentiated, but show little or no morphological differences. This study investigated whether volatile components can be used to distinguish the cryptic species within the Conocephalum conicum complex. Thirteen samples were included in this study representing four cryptic species (A, F, J, L) and the recently described Conocephalum salebrosum (formerly cryptic species S) detected in a worldwide collection. Results received from GC-MS analyses showed some differences between samples, indicating the existence of chemical polymorphism. It is evident from both statistical analyses (CA and PCA), that cryptic species L appears to be the most differentiated species, with the volatile components not significantly shared with the rest of the types. The most characteristic compound of this type is the sesquiterpene alcohol, conocephalenol. Distinction between other examined cryptic species were also indicated. However species F and J, as well as species A and C. salebrosum, share a great similarity in their volatile composition and are grouped together in both CA and PCA. Despite their similarities, we were able to find chemical markers which can describe each species. Cubebol is characteristic for C. salebrosum, while cryptic species A produces (E)-methylcinnamate. The presence of a large amount of the monoterpene hydrocarbon, sabinene, is characteristic for cryptic species J. In one of the analyzed specimens belonging to the cryptic species F, a large amount of cyclocolorenone was detected. Chemical differentiation was correlated with the geographical distribution of the analyzed samples.

Chromatographic analysis of ginsenosides occurring in the roots of American ginseng ( Panax quinquefolium L.) and in Asian ginseng ( Panax ginseng C.A. Mayer) preparations

The object of these investigations was comparative analysis of the composition of ginsenosides occurring in roots of Panax quinquefolium L. cultivated in the Department of Industrial and Medical Plants Agriculture, University of Lublin (Poland) and on the Inberger Ginseng Farm in Wisconsin (USA), and in concentrate and preparations from Panax ginseng C.A. Mayer. TLC analysis revealed differences between the content and composition of ginsenosides in extracts from P. ginseng and P. quinquefolium. American ginseng is characterized by higher concentrations of Rb1 and Re ginsenosides whereas the amount of Rg1 ginsenoside in American ginseng is considerably less than in Asian ginseng. The investigations also showed that roots of American ginseng cultivated in Poland and encapsulated American ginseng roots cultivated in the USA have identical composition. This proves the suitability for pharmaceutical purposes of raw material cultivated in Poland

Chemical Constituents of Bryophytes: Structures and Biological Activity

Comparatively little attention has been paid to the bryophytes for use in the human diet or medicine in spite of the presence of 23 000 species globally. Several hundred new compounds have been isolated from the liverworts (Marchantiophyta), and more than 40 new carbon skeletons of terpenoids and aromatic compounds were found. Most of the liverworts studied elaborate characteristic odiferous, pungent, and bitter-tasting compounds, of which many show antimicrobial, antifungal, antiviral, allergic contact dermatitis, cytotoxic, insecticidal, anti-HIV, plant growth regulatory, neurotrophic, NO production and superoxide anion radical release inhibitory, muscle relaxing, antiobesity, piscicidal, and nematocidal activities. The biological effects ascribed to the liverworts are mainly due to lipophilic sesqui- and diterpenoids, phenolic compounds, and polyketides, which are the principal constituents of their oil bodies. Some mosses and liverworts produce significant levels of vitamin B2 and tocopherols, as well as prostaglandin-like highly unsaturated fatty acids. The most characteristic chemical phenomenon of the liverworts is that most of the sesqui- and diterpenoids are enantiomers of those found in higher plants. In this review, the chemical constituents and potential medicinal uses of bryophytes are discussed.

Fingerprinting of secondary metabolites of liverworts: chemosystematic approach.

The relationship between various types of plants can be predicted based on the similarity in the chemical substances present in them. Compounds that belong to the category of secondary metabolites are of great value in identifying such relationships. Additionally, results from the chemical investigations, together with the other biological or genetic information, can help to understand real relationships among the taxa. Liverworts are small spore-forming plants with simple morphological organization. On the other hand, many liverwort species demonstrate wide geographical distribution and grow under diverse ecological conditions. Because of this, the identification of these plants is especially challenging. One of the outstanding features of the liverworts is their chemistry. They produce a wide array of secondary metabolites, mainly terpenoids and aromatic compounds. Many of these compounds are characterized by unique structures, and some have not been found in any other plants, fungi, or marine organisms. The potential use of chromatographic fingerprinting of the liverworts, as complementary to morphological and genetic information, to resolve the taxonomic problems at the species, genus, and family levels are discussed.

Bryophytes: liverworts, mosses, and hornworts: extraction and isolation procedures.

There are more than 20,000 species of bryophytes in the world. Among them, almost of liverworts (Marchantiophyta) possess beautiful blue, yellow colored or colorless cellular oil bodies from which over several hundred new terpenoids, acetogenins, and aromatic compounds including flavonoids with more than 40 new carbon skeletons have been isolated. Some of the isolated compounds from liverworts show antimicrobial, antifungal, antiviral, allergenic contact dermatitis, cytotoxicity, insect antifeedant and mortality, antioxidant, nitric oxide (NO) production and plant growth inhibitory, neurotrophic and piscicidal activity, tublin polymerization inhibitory, muscle relaxing, and liver X-receptor (LXR)α agonist and (LXR)β antagonist activities, among others. The bio- and chemical diversity, chemical analysis of bryophytes including extraction, distillation, purification, TLC, GC and GC-MS, and HPLC analysis of oil bodies of liverworts are surveyed.