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17

Comparative Phytochemistry and Chemotaxonomy

Prathamesh A. Marne, Anil T. Pawar, Amol A. Tagalpallewar, Akshay M. Baheti
Department of Pharmaceutical Sciences, School of Health Sciences and Technology, Dr. Vishwanath Karad MIT World Peace University, Pune, India

17.1 Introduction

The initial widely accepted classification for plants was developed by Swedish botanist Carolus Linnaeus and is known as the artificial system. Linnaeus also introduced the binomial nomenclature system, which laid the groundwork for modern nomenclature systems. Based on their traits, organisms were assigned two names: genus and species. He categorized living beings into three distinct domains: the mineral kingdom, called as Regnum Lapideum, the animal kingdom, known as Regnum Animale, and the plant king­dom, designated as Regnum Vegetabile. Based on the repro­ductive organs, or the number of stamens and pistils, he further divided plants into 24 phyla. Six classes of animals were recognized: Aves, Amphibians, Mammals, Insecta, Pisces and Vermes. The four classes of minerals are called Petrae, Minerae, Fossilia, and Vitamentra. During the initial decades of the nineteenth century, there was a gradual tran­sition from the Linnaean system to natural classification systems. These new systems aimed to utilize all pertinent data to organize plants into categories based on their overall resemblance. The natural system of classification distin­guishes between species according to their common mor­phology, genetic makeup, and evolutionary connections. It is a well-rounded classification system because it takes into account both an individual’s genetic makeup and physical characteristics. In 1813, Augustin Pyramus De Candolle introduced the term “taxonomy” for the first time. Its roots lie in Greek, where it denotes the systematic organization of living organisms. Specifically, “taxi” conveys the idea of arrangement, while “nomos” pertains to law or rule [1].
It primarily addresses the naming, categorization, and identification of plants. Following the release of Darwin’s On the Origin of Species in 1859, biological classification adopted evolutionary relationships as its foundation, giving rise to classifications known as phylogenetic [2]. The infor­mation and data used in current taxonomy come from sev­eral fields of botany, including morphology, anatomy, embryology, palynology, cytology, photochemistry, genetics, and physiology. Earth harbors a vast array of plant species, the majority of which offer significant benefits to humanity. These plants exhibit considerable diversity in their habitats, lifespans, morphologies, modes of nourishment, and repro­ductive strategies. Several scientists use various plants in their research. Because of this, taxonomy is necessary to promote improved communication and accurate plant identification.

17.2 Chemotaxonomy

Chemotaxonomy, alternatively called chemosystematics, attempts to classify organisms and distinguish them by analyzing the differences among them and the resem­blances between the biochemical compositions in them [3]. Chemotaxonomy investigates how chemical compounds or groups of chemicals produced by living organisms are dis­tributed among related or potentially related plant species [4]. The examination of phytochemical diversity among plants is the central concern of chemotaxonomy. Pioneers in this field were individuals who utilized plants for medic­inal purposes or recognized their significance in creating
334 17 Comparative Phytochemistry and Chemotaxonomy
substances, such as fish toxins, arrow poisons, and ordeal poisons. “Folk taxonomies,” grounded in innate human instincts and based on observable plant characteristics like edibility, taste, color, smell, and medicinal value, have his­torically provided subjective foundations for classification. These variations have been employed for categorization purposes.
Chemotaxonomy is primarily divided into two catego­ries: macromolecular and micromolecular. Micromole­cular data relies on secondary metabolites (SMs), which are produced by all living organisms. These SMs originate from primary metabolites (PMs) and form the cornerstone of this classification [5]. PMs are crucial for plant func­tions, such as growth, development, and strain adapta­tion. A key role is played by them in essential metabolic processes like photosynthesis, nutrient acclimatization, and respiration [6]. The biosynthesis pathways and chem­ical structures of SMs are helpful in classification since they are often distinctive to taxonomically related organ­isms. It is possible to examine fresh or dried samples using this classification method [7]. The simple working meth­odology of this classification approach gives advantages over the morphological classification. Because chemotax­onomy uses sophisticated analytical techniques to detect even minute amounts of substances, it has a higher sensi­tivity and an easier working methodology. Advanced ana­lytical techniques, such as gas chromatography (GC), high-performance (HP) or ultra-performance (UP) liquid chromatography (LC), and capillary electrophoresis (CE), are frequently employed alongside analytical methods like mass spectrometry (MS), nuclear magnetic resonance (NMR), and near-infrared (NIR) spectrometry. The main category of SMs, crucial for chemotaxonomy, includes alkaloids, glycosides, phenolics, and terpenoids. In plant taxonomy, macromolecular methodologies encompass serology, amino acid sequencing, allozyme electrophore­sis, and DNA or DNA/RNA hybridization, along with the mapping and sequencing of DNA. Recognizing large flowering plants is relatively uncomplicated, but distin­guishing small flowers, especially those of grasses, pre­sents significant challenges. The limited attention to plant morphology has resulted in a shortage of skilled taxono­mists. Additionally, obstacles to plant identification include insufficient familiarity with classification princi­ples, and terminology, as well as the absence of authentic herbaria for comparison [8]. Accurate identification and a steady supply of uniform plant material are necessary to fully utilize the plants for commercial or industrial purposes. To support economic activity, biologists, molec­ular scientists, and farmers must work together. Correct plant identification and undoing of modifications are
fundamental to all of them. One of the key instruments to address this issue is chemotaxonomy.

17.3 Chemical Markers in Chemotaxonomy

Two types of chemicals are produced by plant cells: PMs and SMs. PMs occur to be essential in basic plant functions, such as growth and metabolism. They include carbohy­drates, which are sugars and starches that provide energy; lipids, which are fats used for storing energy; and proteins, which are essential for various cellular processes. In con­trast, SMs, which originate from PMs, do not participate directly in metabolic processes. This group includes pheno­lics, alkaloids, essential oils, steroids, and tannins [9].

17.3.1 Primary Metabolites

PMs are fundamental substances generated through meta­bolic pathways, playing pivotal roles in various biological processes, such as cellular functions, development, and reproductive functions. Major PMs encompass carbohy­drates, lipids, proteins, and nucleic acids. Plant PMs also yield enzymes that are crucial for respiration and photo­synthetic processes. Furthermore, PMs play indispensable roles in constructing basic cell structures, including chitin and peptidoglycan for cell walls, proteins for cytoskeletons, and phospholipids for cell membranes. Nucleic acid PMs form the essential components of DNA and RNA [10, 11].

17.3.2 Secondary Metabolites

Plant SMs are categorized into distinct groups based on their chemical structures and functional groups. Terpenes, sterols, carotenoids, phenolic compounds, phytoalexins, alkaloids, glycosides, flavonoids, and hydrocarbons are some of these classes [12].
17.3.2.1 Glycosides
An entity of glucose coupled to an aglycone makes up glyco­sides. The glycone (sugar), aglycone (non-sugar), and type of glycosidic bond form the glycosides. The class of glyco­sides contain molecules in which a sugar moiety is joined to an aglycone molecule by an O–, S–, N–, or C–glycosidic bond. Glycosides are classified based on their glycosidic linkages into O-glycosides, C-glycosides, S-glycosides, and N-glycosides. O-glycosides, the most prevalent type found in plants, have their glycone and aglycone components con­nected through an oxygen atom. C-glycosides are resistant to hydrolysis because the glycone and aglycone portions
17.4 Methods in Chemotaxonomy 335
are linked by a carbon atom (carbon-based linkage). In S-glycosides, the glycone and aglycone components are linked by a sulfur atom (sulfur acts as a linker; aglycones must have –SH groups). In N-glycoside, a nitrogen atom con­nects the glycoside’s glycone and aglycone components (the aglycone must have –NH group) [13].
17.3.2.2 Alkaloids
Alkaloids represent the category of chemical compounds that occur naturally and are characterized predominantly by the presence of basic nitrogen atoms [14]. Approximately 20% of the SMs identified in plants are alkaloids. Amino acids are the primary biosynthetic source of alkaloids. Tryptophan, lysine, and tyrosine are examples of amino acids that function as building blocks for nitrogenous SMs. True alkaloids, including compounds like atropine and nicotine, are characterized by the presence of a nitrogen­containing heterocyclic ring and are derived from amino acids. On the other hand, proto-alkaloids, exemplified by adrenaline and ephedrine, also contain a nitrogen atom from an amino acid but lack its incorporation into a hetero­cyclic ring.
17.3.2.3 Terpenoids
Terpenes are composed of isoprene units containing five carbons each. These units determine the classification of terpenes. Monoterpenes are structured from a pair of iso­prene units, yielding the molecular composition C
10H16
Sesquiterpenes, on the other hand, comprise three iso­prene units, resulting in the chemical formula C
15H24
Furthermore, diterpenes are created from four isoprene units, giving rise to the molecular formula of C
20H32
Triterpenes, composed of six isoprene units, exhibit the formula C
. Compounds consisting of seven isoprene
30H48
units are termed sesquiterpenes and bear the formula
. Tetraterpenes, formed from eight isoprene units,
C
35H56
possess the molecular composition C
17.3.2.4 Phenolic Compounds
40H64
[15].
Phenolic compounds stand as a paramount category among plant SMs, distinguished by the existence of one or more phenol groups. Ubiquitous in plants, these com­pounds exert significant influence on their color, flavor, and taste. The shikimate metabolic pathway offers a possi­ble avenue for the synthesis of phenolic compounds. Phenolic compounds are classified into flavonoids, tan­nins, and simple phenolics based on their structural fea­tures [16].
Over 4000 distinct flavonoids derived from plants have been found to date. These are most frequently seen in green plants, where they are mostly found as glycosides in the
stems, roots, leaves, and flowers. Flavonoids consist of two benzene rings and are categorized based on the oxidation level of the central ring. These categories include fla­vanones, flavanonols, flavans, anthocyanidins, and isofla­vonoids, each characterized by its distinct chemical structure [17].
Tannins are the category of naturally occurring poly­phenolic compounds with multiple units, including polyhydroxyphenolic groups or their derivatives. These compounds can form complexes with other substances such as minerals, cellulose, and proteins. Tannins fall into two primary categories: hydrolyzable and condensed [18].

17.4 Methods in Chemotaxonomy

Chemotaxonomic studies employ diverse analytical meth­ods to identify and quantify chemical compounds.

17.4.1 Chromatography

Chromatography serves as a valuable quantitative analyti­cal technique, allowing for effective separation within a reasonable timeframe. Chemotaxonomy utilizes various chromatography techniques, such as column chromatogra­phy, thin-layer chromatography (TLC), GC, paper chroma­tography, ion exchange chromatography, gel permeation
.
chromatography, high-pressure liquid chromatography, and affinity chromatography [19]. For volatile substances,
.
GC is utilized. Complex combinations of terpenoids and alkaloids can be identified with significant advantages
.
from the use of GC-MS. For non-volatile and thermally labile substances, high-performance liquid chromatogra­phy (HPLC) is effective. HPLC is also widely utilized in the analysis of nucleic acids and phenolic compounds.
The number and composition of compounds within a sample, whether they are fluorescent, volatile, or of a cer­tain chemical nature, dictate the selection of sensitive and rapid analytical instruments utilized in laboratory settings. Because of the volatile nature of the compounds, gas is employed as a carrier medium in gas-liquid chromatogra­phy (GLC), whereas liquid solvents are used as a medium in TLC and HPLC because the compounds are soluble [20].

17.4.2 Spectroscopy

Spectroscopic methods are widely used to precisely ana­lyze the chemical structure of an analyte. Each method allows the molecule to interact with the electromagnetic radiation. Chemical substances have properties to inter­act with radiation’s electric and magnetic characteristics.
336 17 Comparative Phytochemistry and Chemotaxonomy
To identify and describe these substances, scientists look at atoms, bonds, functional groups, a core nucleus, a molecular formula, and a molecular weight. NMR helps to study molecular structures in detail. Infrared (IR) and ultraviolet-visible (UV-Vis) spectroscopy help to find functional groups and conjugated systems in organic mol­ecules. Mass Spectroscopy (MS) accurately determines molecular weights and structures by analyzing the mass­to charge ratio of ions. When combined with chromatog­raphy methods like GC-MS or LC-MS, the MS allows for precise examination of intricate mixtures, aiding in the detection of separate constituents.

17.5 Phytochemical Approach in Chemotaxonomy

17.5.1 Fatty Acids

ering gametophyte samples from 20 bryophyte species found in Siberia. These organisms come from four groups of mosses and four groups of liverworts. The sampling was performed in the cooler seasons, particularly in April and/ or October. They analyzed the fatty acid (FA) content using GC to obtain FA profiles. Thirty-seven FAs were identified; these comprised dicranin, acetylenic monounsaturated, and polyunsaturated fatty acids (PUFAs). All of the studied taxa belonging to the orders Dicranales and Bryales included acetylenic FAs, with dicranin being the most common FA. According to the results of the multivariate discriminant analysis, a species’ taxonomic status and FA composition are connected [21].
An extensive analysis of oils from 21 distinct Pinus spe­cies was conducted by researchers to identify those rich in Δ5-unsaturated polymethylene-interrupted fatty acids (Δ5-UPIFA). By employing GC-FID, GC-MS, and NMR techniques, they thoroughly scrutinized the FA composi­tions, providing a reliable approach to ascertain the pro­portion of Δ5-UPIFA relative to total FA. Taxoleic and bishomopinolenic acids were prevalent across various tax­onomic groups, while pinolenic acid (PNLA) and sciadonic acids were consistently present in all samples. Elevated PNLA concentration was found in Pinus mugo, accounting for 28.3% of the total FAs, whereas Pinus koraiensis dis­played the highest total FA content at 66.8 g/100 g seeds. Principal Component Analysis illustrated that species belonging to the Pinus subsections could be clustered together due to similarities in their FA compositions [22].
It is challenging to distinguish between several species of freshwater green microalgae in the family Selenastraceae due to their subtle physical differences. Many species in the
family cannot be distinguished from one another using the diacritical features of traditional morphological classifica­tion. The application of chemotaxonomy, which depends on fatty acid methyl ester (FAME) analysis, has effectively resolved ambiguities that persist unresolved by other tech­niques. An investigation was conducted on eight genera and 15 species of green coccoid microalgae using the direct transesterification-gas chromatography-mass spectrometry (DT-GC-MS) method. Substantial differences were noted in FA compositions among various strains and species. The categorization based on strains elucidated 97% of the observed diversity, whereas species differentiation contrib­uted to 93% of the variability. Notably, the presence of the C18 FAs 18:3ω3 and 18:4ω6 was identified as a distinctive characteristic of the Selenastraceae family [23].
GC was utilized to assess the FA composition of 59 differ­ent genetic variants spanning 14 distinct Coffea species sourced from various regions, including Cameroon, Ivory Coast, Angola, the Comoro Islands, the Central African Republic, Kenya, the Republic of the Congo, Mozambique, and Tanzania. Within the chromatograms of these 59 geno­types, 18 peaks were detected. Notably, no single peak could be attributed to a specific Coffea species or cluster thereof. Consequently, only 10 FAs with relative abundances exceeding 0.1% were considered for further multivariate analysis. Among these, the prevailing FAs observed across all species were palmitic, stearic, oleic, and linoleic acids [24].
The FA composition of 12 Brassica species (Brassicaceae) was examined via gas chromatography with flame ioniza­tion detection (GCFID) to aid in chemotaxonomic classifica­tion. Three distinct groups were identified based on the ratios of C18 : 1 (n~7)/(n~9). The initial cluster encompasses
Brassica rapa, Brassica napus, and Brassica tournefortii, with Eruca sativa closely associated with Brassica napus. Raphanus sativus, Sinapis alba, and B. tournefortii form the second cluster. The final group, consisting of Brassica nigra, Brassica carinata, and Brassica juncea, displays no resem-
blance to the other species [25]. GC-MS analysis was utilized to explore the FA content of seed oil from 23 Stachys (Labiatae) species [26]. Primary constituents include linoleic acid (27.1–64.3%), stearic acid (trace to 5.2%), palmitic acid (4.3–9.1%), oleic acid (20.25–48.1%), and 6-octadecynoic acid (2.2–34.1%). The latter compound may serve as a chemotax­onomic marker for the Stachys genus.

17.5.2 Alkaloids

Zhang and team conducted a study where 16 known com­pounds extracted from the ethanolic extract of Glehnia littoralis roots were identified and characterized. These compounds include three β-carboline alkaloids, five phe­nolic acids, four phenylpropanoids, three polyacetylenes,
17.5 Phytochemical Approach in Chemotaxonomy 337
and one FA. Among the compounds identified, (1S,3S)­1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid, (3S)-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid, (1R, 3S)-1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid, (S)-phenyllactic acid methyl ester, (S)-phenyllactic acid, salicylic acid, 4-hydroxyphenethyl alcohol, and 9-hydroxystearic acid haven’t been previously documented in any Umbelliferae family species. Furthermore, isop­impinellin, catechol, and dibutyl phthalate were isolated for the first time from the Glehnia genus. These findings hold significant chemotaxonomic implications, offering valuable markers for characterizing G. littoralis [27].
The Leguminosae genus Ulex is distinguished by the presence of quinolizidine alkaloids, such as cytisine, N-methylcytisine, as well as jussiaeiines A, C, and D. These compounds are important in chemotaxonomy. In the Menispermaceae family, isoquinoline alkaloids have prev­alence and serve as a valuable tool in chemotaxonomy. A rarely described pyrimidine-beta-carboline-type alkaloid is particularly significant for the chemotaxonomy of the Annona genus (Annonaceae). Tropane alkaloids have been employed in the chemotaxonomic analysis of the pantropi­cal plant genus Merremia (Convolvulaceae) [28]. Similarly, within the Boraginaceae family, pyrrolizidine alkaloids are important compounds that may act as chemotaxonomic markers [29].
In a study assessing 34 species of Paullinia and related genera for purine alkaloids (PuA), which are important markers in chemotaxonomy, only Paullinia pachycarpa exhibited positive results alongside the previously identi­fied Paullinia cupana and Paullinia yoco. Upon closer examination, it was discovered that theobromine was detectable in the stem, leaves, and flowers of P. pachycarpa. Notably, the concentration of theobromine in the stem cor­tex exhibited a significant increase toward the plant’s base [30]. Chemotaxonomic investigations indicate that out of all Sceletium species belonging to the Aizoaceae family, only some of them possess the alkaloids of mesembrine­type commonly found in the genus. Therefore, precise identification of the particular Sceletium species is essen­tial to confirm the correct alkaloidal composition required in manufacturing and assurance of the quality of products utilizing this type of botanical substance.

17.5.3 Phenolic Compounds

Regarding the genus Aletris’s boundaries, there is a lot of debate. Initially, the genus Aletris was classified under the Liliaceae family within the order Liliales. Recent studies propose that Aletris, alongside its counterparts Lophiola, Metanarthecium, Narthecium, and Nietneria, may require reclassification from the Liliaceae family to
the Nartheciaceae family within the Dioscoreales order. Moreover, Aletris and Metanarthecium appear to be gen­era with distant relationships. It has also been observed that Metanarthecium and Aletris are genera with distant relations. These findings underscore the contentious and intricate connections within the Nartheciaceae, particu­larly between Aletris and Metanarthecium.
The findings showed that Aletris spicata and other Dioscoreales plant species share certain comparable com­ponents (5-hydroxymethyl furfural, apigenin). It is pos­sible to identify (2R,3R)-2,3-dihydro-3,5-dihydroxy-7, 40
-dimethoxyflavone, 5-hydroxy-7,8,40-trimethoxyflavone, sinapaldehyde, 3-methoxy-4-hydroxycinnamic aldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxyaceto­phenone, and amentoflavone as distinctive chemical com­ponents of the genus Aletris [32].
Upon examination of Stachys species flourishing in Greece, it was observed that Stachys ionica exhibits a unique chemical composition. While other Greek varieties are rich in flavonoids originating from chrysoeriol, S. ion- ica instead synthesizes derivatives of isoscutellarein [33]. Erucoides have a different flavonoid pattern from Diplotaxis muralis, while Diplotaxis acris and Diplotaxis harra have comparable flavonoid profiles. The flavonol composition shows variation between Diplotaxis erucoides and Diplotaxis muralis. In Diplotaxis erucoides, a notable char­acteristic is the presence of a –OCH
group at position 7,
3
accompanied by rhamnetin 3, 3-di-O-glucoside, and glyco­sylation mainly occurring at positions 3 or 7. Conversely, in D. muralis, the –OCH
group is found at position 3′ (isor-
3
hamnetin compounds), with glycosylation predominantly observed at position 3 [34].
Flavonoids are important markers for classifying dif­ferent Iris plants. They have a basic three-ringed struc­ture of isoflavone or flavone. Even though natural flavonoids can be quite different, they typically have sugar attached and O-substitution patterns. Within the A-ring, prevalent occurrences of 5,6,7-tri-O substitution or 5,7-di- substitution patterns are observed, with the substitution of 6,7-methylenedioxy being a notable char­acteristic. Moreover, frequent instances of 2’- or ortho substitution at 4’, along with 3’,4’,5’- tri-ortho- substitu­tion and 3’,4’-, 2’,3’ - or 4’,5’-di-ortho-substitution are observed in the B-ring. The presence of certain chemicals could be suggested as a clue for sorting Iris species, which could be important for classifying them. Notably, the distinctive components of Iris include isoflavones and their glycosides, with representative substances, such as tectoridin, irilin B, tectorigenin, irilone, and irigenin. The distribution pattern of isoflavones in Chinese Iris rhizomes indicates that the majority of species in the subgenus Limniris possess isoflavone aglycones rather
338 17 Comparative Phytochemistry and Chemotaxonomy
than isoflavone glycosides, with Iris tenuifolia, Iris lactea, and Iris bungei standing out due to their exclusive con­tent of isoflavone aglycones. Within the Limniris subge­nus of the Iris genus, which includes species like I.
cathayensis, I. bungei, Iris songarica, I. lactea, and I. tenui- folia, a distinctive occurrence of altered flavonoids
known as peltogynoids can be observed. These peltogy­noids play a significant role as reliable taxonomic mark­ers within this genus [35].
The existence of phenolic chemicals in Euphrasia species (Euphrasia rostkoviana, Euphrasia stricta, and Euphrasia nemorosa) gathered from the wild was investigated by Gawenda-Kempczyńska et al. [36]. They reported that the phenolic component concentration varies greatly amongst the species of Euphrasia. The highest overall concentration of polyphenols and flavonoids is found in E. rostkoviana. E. stricta exhibits the highest levels of phenolic acids, notably protocatechuic, p-coumaric, 5-O-caffeoylquinic, and salicylic acid. These compounds serve as distinguishing chemotaxonomic markers for this species. Specifically, sali­cylic and protocatechuic acid are predominant in E. stricta, while 5-O-caffeoylquinic acid and ferulic acid are chemot­axonomical markers for E. rostkoviana and E. nemorosa, respectively [36].
By employing phytochemical fractionation on the metha­nol extract obtained from Lysimachia. baviensis, researchers have found a couple of new chalcone glycosides, such as bavienside B and bavienside C, along with an original stil­bene or crystalline compound identified as bavienside A. The elucidation of these compounds’ structural features was achieved through the analysis of NMR and HRESIMS spectroscopic data. First discovered in a natural source, the C-acetylstilbene and carbomethyl chalcone structures in compounds bavienside A and bavienside C may serve as sig­nificant indicators for the chemotaxonomy of L. baviensis [37]. Thirteen species of Trifolium (Leguminosae) native to Poland were classified based on the presence of isoflavone aglycones, which are pharmacologically active, including formononetin, daidzein, genistein, and biochanin A [38]. Across various taxonomic ranks, such as family down to species, compounds like naphthodianthrones (e.g. hypericin and pseudohypericin), biflavonoids (e.g. amenoflavone), flavonol glycosides (e.g. isoquercitrin and hyperoside), phloroglucinol derivatives (e.g. hyperforin and adhyper­forin), including xanthones, are known to act as distinctive chemical markers for classification purposes [39].
The taxonomic classification of the extensive Drosera genus has long been a subject of debate. To elucidate the chemotaxonomic placement of 10 Drosera species, repre­senting various subgenera and sections of the genus, the researcher investigated their primary phenolic chemical profiles. The investigation was specifically focused on the
flavonoid composition and derivatives of ellagic acid across various species within the Drosera genus, that are Drosera
burmannii, Drosera hilaris, Drosera spatulata, Drosera ade­lae, Drosera petiolaris, Drosera montana, Drosera pygmaea, Drosera aliciae, Drosera binata, and Drosera dielsiana. It is
noteworthy that all the members of the Drosera section exclusively showcased flavonols of the quercetin type. Drosera peltata displayed the synthesis of flavonols of the gossypetin type, whereas D. binata synthesized flavonols of the 8-methoxyquercetin type alongside quercetin-type fla­vonoids. Additionally, distinct flavonoid patterns were observed in Dictyopygmea and D. petiolaris, belonging to the sections Bryastrum and Lasiocephala, respectively. Both Drosera species exhibited the presence of flavones of the 8-hydroxytricetin type, while D. pygmea was particu­larly remarkable for its elevated concentration of flavones of the tricetin type [40].
The family Anacardiaceae is known for having chemot­axonomic traits such as 7-methoxylated flavonoids [41]. The phytochemical composition examination of Psidium guajava Linn. leaves resulted in the identification and char­acterization of eight triterpenoids, six guavinosides, four flavonoids, and one lignan. Utilizing NMR spectroscopy techniques, all chemical structures were elucidated and fur­ther corroborated through comparison with existing litera­ture data. The findings indicated that close chemotaxonomic links had been observed among the Myrtaceae, Asteraceae, and Lamiaceae plant families. Guavinosides C–F emerged as distinctive identifiers for differentiating P. guajava, whereas guavinosides A–F could serve as significant mark­ers within the Myrtaceae family in chemotaxonomy [42].
The chemical composition of three Amaranthus species –
Amaranthus blitum (AB), Amaranthus hybridus (AH), and Amaranthus caudatus (AC) – were investigated using
LC-MS/MS (liquid chromatography-tandem mass spec­trometry). A total of 41 distinct compounds were identi­fied, showcasing differences in both their occurrence and levels across the species. Notably, flavonoid glycosides and hydroxycinnamoyl amides emerged as the key metabolites, facilitating the chemotaxonomic differentiation of each species. The glycosides isorhamnetin and tricin were found to be exclusively present in AC, providing valuable chemo­taxonomic markers for this species. The majority of metab­olites were shared by the AB and AH profiles but in differing amounts. N-trans-feruloyl-4-O-methyldopamine, dicaffeoylquinic acids, nicotiflorin, and adenosine are a few of them. N-coumaroyl-ʗ-tryptophan and kaempferol dirhamnoside, on the other hand, were unique to AB and distinguished it from AH [43].
Researchers employed an HPLC-PDA system to assess the utilization of Deguelia rufescens var. urucu, known as “timbo,” and Deguelia utilis as sources of rotenone in
17.5 Phytochemical Approach in Chemotaxonomy 339
insecticide formulations. Hierarchical cluster analysis (HCA) was employed to scrutinize the data. A linear rela­tionship between these species was established by quanti­fying their primary rotenoids. For D. rufescens var. urucu, the ratio of rotenone to deguelin concentrations is 2 : 1, whereas for D. utilis, it is 1 : 0.8. These findings could aid in the taxonomic identification of these species by helping to differentiate them [44].
The stigma of Crocus sativus L. is highly prized as a pre­mium spice because of its abundant chemical constituents, including safranal, picrocrocin, a monoterpenoid gluco­side, and the carotenoids crocetin and crocin. However, a significant portion of saffron crocus byproduct is wasted, as only the stigma is utilized commercially. To address this issue, the researcher collected saffron crocus flowers from 40 different regions across Iran. Following that, an examination was conducted on both the outer floral com­ponents and the male reproductive organs utilizing high­performance liquid chromatography with diode array detection (HPLC-DAD). This analytical approach enabled the determination and measurement of seven essential substances, among which are quercetin-3-O-sophoroside, kaempferol-3-O-glucoside, safranal, crocin, and crocetin. Three types of flavonol glycosides were found in tepal (outer floral part) and stamen samples. It was observed that the main type of flavonoid present in the outer floral parts
−1
ranged from 62.19 to 99.48 mg g
of kaempferol-3-O­sophoroside. Comparatively, the stamen samples exhibited lower flavonoid content than the tepals. The predominant compound observed in the stamens was kaempferol-3-O­glucoside, with concentrations ranging from 1.72 to
−1
7.44 mg g
. Notably, none of the examined samples con­tained crocin, crocetin, picrocrocin, or safranal [45]. The examination encompassed the floral pigments of 70 Crocus species, along with 43 cultivars and six hybrids that have been generated. Crocus appears to have six flavonol glyco­sides and three malonated anthocyanins that are all unique to the plant. As flavonoids were present in every taxon under investigation and because these compounds were all broadly distributed within the genus, they can be employed as distinctive markers for this genus. Chemical structures within the genus, especially the anthocyanins, have a diverse distribution that makes it possible to employ them as chemotaxonomical identifiers [46].
Analysis of Ficus deltoidea, a medicinal plant was inves­tigated by LC-MS metabolomics to examine the effect of varietal, geographic, and environmental factors. Seven dif­ferent varieties displayed distinct chemical compositions characterized by the predominant flavonoids identified in the 85% methanolic extract. These varieties were grouped into three main categories using PCA/HCA modeling. Chemotype-a was exemplified by var. trengganuensis and var. intermedia, chemotype-b consisted of var. angustifolia,
and chemotype-c included var. deltoidea, var. kunstleri, and var. motleyana. Despite varying geographical locales and cultivation conditions, the core composition remained con­sistent across these varieties. The differentiation of the three chemotypes was facilitated by 15 flavone glycoside markers. Schaftoside, isoschaftoside, and vicenin-3 were identified in both var. trengganuensis and var. intermedia. Oxypeucedanin hydrate, a furanocoumarin marker distin­guishing var. intermedia from var. trengganuensis, was observed in the UV chromatograms of all seven varieties. Vitexin and isovitexin acted as distinct markers for var.
angustifolia and chemotype-c, respectively. Notably, var. deltoidea (chemotype-c) could be further characterized by
the presence of rhoifolin [47].
A rapid reversed-phase (RP) HPLC method was employed for the simultaneous separation and analysis of flavonoids and phenolic acids in eight taxa of Plantago (Plantaginaceae) found in Croatia [48]. Differences in the concentrations of phenolic compounds were noted among various species. For example, in P. lagopus, hyperoside lev- els reached up to 0.020% of dry leaf weight, while in P. hol- osteum ssp. holosteum, quercitrin levels reached up to
0.013%. Quercetin was detected in P. holosteum ssp. scopu-
lorum at levels of up to 0.028%, rutin up to 0.024% in P. argentea, and caffeic acid up to 0.046% in P. coronopus.
Isoquercitrin was exclusively found in P. argentea, recorded at 0.020%, while isochlorogenic acid remained undetected in all analyzed species. Significant differences in polyphe­nolic compound levels among various Plantago species were revealed by multivariate analyses like UPGMA (Unweighted Pair Group Method with Arithmetic Mean) and PCA (Principal Component Analysis). These com­pound profiles show potential as chemotaxonomic mark­ers, providing a comprehensive approach to exploring the diverse genus Plantago. Among 20 different cultivars of ber (Ziziphus mauritiana; Rhamnaceae), variations were observed in the levels of gallic, vanillic, tannic, caffeic, chlorogenic, cinnamic, and ferulic acids, underscoring their significance as essential chemical markers for taxo­nomic classification [49].
The significance of phenolic acids and flavonoids in chemotaxonomy is particularly notable when differentiat­ing diploid taxa within the Achillea millefolium L. assem­blage (Asteraceae) [50]. A chemotaxonomic investigation was undertaken encompassing 16 distinct Vicia species, comprising cultivated and wild variants. Ultraperformance liquid chromatography-mass spectrometry (UPLC-MS) coupled with chemometric analysis was employed to exam­ine seed accessions within the Vicia genus. Across the Vicia accessions studied a comprehensive total of 89 metabolites were identified. When differentiating between Vicia species, particular metabolites like FAs, flavonoids, and anthocyanins were identified as notable chemotaxonomic
340 17 Comparative Phytochemistry and Chemotaxonomy
indicators. Notably, Vicia faba samples displayed increased levels of FAs, whereas Vicia parviflora showcased the high- est concentrations of flavonoids. Anthocyanins played a pivotal role in discerning between Vicia hirsuta and Vicia sepium [51].

17.5.4 Essential Oils

Six species of Gingidia from the Umbelliferae family, found in New Zealand and Australia, were identified as having important chemotaxonomic markers in the form of pri­mary monoterpenes, such as β-phellandrene, limonene, and γ-terpinene, along with phenylpropanoids like estragole, (E)-anethole, and myristicin [52].
The researcher investigated the composition and chemi­cal properties of four distinct types of blackcurrants grown in Serbia: Ben Sarek, Ometa, Ben Lomond, and Ben Nevis. These different cultivars displayed varying oil yields, rang­ing from 1.2 to 2.0% when buds were harvested at two dis­tinct growth stages, with Ometa exhibiting the highest output. Examination of the oils through GC-FID and GC/ MS methods revealed eight primary components: α-pinene (1.6–5.4%), sabinene (1.9–38.4%), d-car-3-ene (13.0–50.7%), β-phellandrene (2.9–18.0%), terpinolene (6.6–11.9%), ter­pinen-4-ol (0.9–6.6%), β-caryophyllene (3.8–10.4%), and α-humulene (0.2–4.1%). The Ometa variety predominantly yields essential oils abundant in sabinene, whereas the Ben Nevis variety is distinguished by its production of δ-car-3­ene type oils. Conversely, the Ben Lomond variety is distin­guished by its high content of β-phellandrene in the oils it produces. Finally, the oils from the Ben Sareks variety exhibit an intermediary composition, showcasing elements of both sabinene and δ-car-3-ene types with relatively low levels of β-phellandrene [53].
The rhizome of Nardostachys grandiflora, acquired from Jaljale, Nepal, exhibited an essential oil output of 1.4%. Analysis of the oil identified the existence of 72 elements, constituting 93.8% of the overall composition. In the essen­tial oil from N. grandiflora rhizomes, there was 9.4% calar­ene, 6.0% nardol A, 11.6% 1(10)-aristolen-9β-ol, 7.1% valerena-4,7(11)-diene, 5.6% valeranal, 7.9% jatamansone, and 5.7% cis-valerinic acid. Remarkably, the chemical com­position of the rhizome oil from Nepalese N. grandiflora significantly differs from that of its Indian, Chinese, and Pakistani counterparts. Additionally, 1(10)-aristolen-9β-ol was confirmed to be present in the N. grandiflora oil [54].
The chemical makeup of essential oils from oleogum res­ins of Boswellia carteri (Somalia), Boswellia papyrifera (Ethiopia), Boswellia serrata (India), and Boswellia rivae (Ethiopia) was studied using GC-MS testing to identify components that could be used as markers for classifying these species. By analyzing GC-MS peak regions, the total
ion current peak areas provided accurate estimates of rela­tive concentrations. The main diterpenic constituents iden­tified in the oleogum resin oils from B. carteri and B. serrata were isoincensole and isoincensole acetate, indicating simi­lar chemical profiles. In contrast, the oleogum resin oil from B. papyrifera was characterized by the presence of n-octanol and n-octyl acetate, along with diterpenic compounds like incensole and incensole acetate. Meanwhile, the primary constituents in the oleogum resin oil from B. rivae included hydrocarbons and oxygenated monoterpenes [55].
The essential oil derived from B. carteri was identified to contain key components like α-pinene, myrcene, limonene, and α-cedrene, comprising 15.1, 8.2, 18.2, and 6.1%, respec­tively. Through comparative analysis of the GC-MS profile of B. serrata resin oil, similarities were found with the B. carteri sample. However, the notable presence of methyl­chavicol (6.7%) and α-thujene (29.7%) distinguishes B. ser- rata as unique chemotaxonomic markers. In the essential oil of B. papyrifera, the main component was identified as n-octyl acetate (63.5%), followed by n-octanol (17.8%) and limonene (4.7%). Minor constituents included α-pinene (2.1%), verticilla-4,7,11-triene (2.3%), incensole acetate (1.7%), and incensole (0.7%). Analysis of the oleogum resin oil of B. rivae revealed limonene (28.0%), 3-carene (15.7%), α-pinene (13.3%), and trans-verbenol (5.8%) as the most prevalent elements, which are indicative of their chemot­axonomic classification [55].
The primary components of the oils extracted from Teucrium polium (Lamiaceae) and Teucrium montanum were sesquiterpenes, constituting 64.3 and 72.7%, respec­tively. The predominant constituents were identified as Germacrene D (31.0%) and d-cadinene (8.1%). In contrast, the oil of Teucrium scordium ssp. scordioides was chiefly characterized by the monoterpene menthofuran (11.9%), thereby distinguishing this species from other Teucrium taxa [56]. It is possible to distinguish between Pseudowintera (Winteraceae) species using the sesquiterpene dialdehyde concentrations [57]. Pseudowintera axillaris demonstrated significant amounts (ranging from 2.2 to 6.9% of leaf dry weight) of paxidal, whereas Pseudowintera insperata speci­mens showcased high levels (ranging from 3.1 to 6.9% of leaf dry weight) of coumarate. In the New Zealand context, Pseudowintera colorata samples collected from various locations exhibited variable concentrations of polygodial (ranging from 1.4 to 2.9%) and 9-deoxymuzigadial (ranging from 0 to 2.9%).
Essential oils from four types of Thuja plants grown in Poland – Thuja occidentalis “globosa,” T. occidentalis “aurea,” Thuja plicata, and T. plicata “gracialis” – were studied using GC and GC-MS methods. The examination found 31 compounds in T. occidentalis “globosa,” making up 96.92% of the entire oil. In T. occidentalis ‘aurea,’