1. IntroductionMost of naturally occurring substances in their structure have one or more acidic or basic groups. Such compounds appear widely in different areas, such as the environment, food, plant extracts, biological fluids, and drugs [1,2]. Therefore, it is of crucial importance to develop efficient methods for the analysis of these compounds in several domains such as clinical analysis, quality control, therapeutic monitoring, toxicological analysis, and metabolism studies. Among these compounds are alkaloids, which are weak organic bases. Alkaloids are pharmacologically active compounds widely used as pharmaceuticals and synthesised as secondary metabolites in plants. Many of these compounds are strongly toxic. For diagnosis and prognosis of such poisonings, analytical methods for detection and quantification of the respective toxic alkaloids are required in clinical and forensic toxicology. Therefore,
they are often subject of scientific interests and analysis. Since alkaloids are basic compounds that appear in aqueous solutions as ionized and unionized forms, they are difficult for chromatographic separation for peak tailing, they have poor system efficiency, poor separation and poor column-to-column reproducibility. Reversed-phase (RP) chromatography continues to dominate applications of high-performance liquid chromatography (HPLC). The majority of silica based stationary phases are produced by reacting porous silica particles with an appropriate silane. Silanol groups (-Si-OH) on the silica gel surface are bonded in this reaction but steric effects prevent the reaction of only part of all the silanols. Further reaction with a short silane (endcapping) eliminates the most accessible silanol groups remaining from the initial bonding but typically does not substantially alter the total concentration of unreacted silanols. These residual silanols can then interact with basic compounds, frequently leading to inferior separations, peak symmetry
Received 29 October 2011; Accepted 27 January 2012
Keywords: Alkaloids • Thin layer chromatography • High performance liquid chromatography • Normal phase system • Reversed phase system
Alkaloids are biologically active compounds widely used as pharmaceuticals and synthesised as secondary methabolites in plants. Many of these compounds are strongly toxic. Therefore, they are often subject of scientific interests and analysis. Since alkaloids - basic compounds appear in aqueous solutions as ionized and unionized forms, they are difficult for chromatographic separation for peak tailing, poor systems efficiency, poor separation and poor column-to-column reproducibility. For this reason it is necessity searching of more suitable chromatographic systems for analysis of the compounds.
In this article we present an overview on the separation of selected alkaloids from different chemical groups by liquid chromatography thus indicating the range of useful methods now available for alkaloid analysis. Different selectivity, system efficiency and peaks shape may be achieved in different LC methods separations by use of alternative stationary phases: silica, alumina, chemically bonded stationary phases, cation exchange phases, or by varying nonaqueous or aqueous mobile phase (containing different modifier, different buffers at different pH, ion-pairing or silanol blocker reagents). Developments in TLC (NP and RP systems), HPLC (NP, RP, HILIC, ion-exchange) are presented and the advantages of each method for alkaloids analysis are discussed.
and systems efficiency [3]. Protonated basic compounds can interact with residual silanol groups of the stationary phase, as shown in the equation:
XH+ + SiO-Na+ ↔ Na+ + SiO-XH+ (1)
Because of that ionic analytes’ retention mechanism is mixed and composed of ion-exchange mechanism with the show kinetics and mass transfer and hydrophobic interactions with much faster kinetics and mass transfer. It gives rise to peak tailing [4]. For this reason, it is necessary to search for more suitable chromatographic systems for analysis of theses compounds. A great variety of analytical techniques have been applied to the determination of different alkaloids, and liquid chromatography is the most frequently used method nowadays. The so-called silanol effect on silica based stationary phases has still been one of the major topics of chromatographic studies even after the development of advanced stationary phases that were supposed to provide symmetrical peaks for basic compounds.
2. Occurrence and medical significance of some alkaloidsIndole is an aromatic heterocyclic organic compound. It has a bicyclic structure, consisting of a six-membered benzene ring fused to a five-membered nitrogen-containing pyrrole ring. Indole alkaloids are biogenetically derived from tryptophan. These alkaloids contain two nitrogen atoms, one of which is contained within the five-membered part of indole nucleus.
Indole alkaloids constitute an important class of natural products which include a large number of biologically important substances such as antitumor alkaloids (vinblastine, vincristine, ajmaline and reserpine), cardioarrithmic alkaloid (ajmalicine) the blood pressure lowering substances (reserpine), and hallucinatory lysergic acid and its derivatives. Some indole alkaloids are strongly toxic (strychnine), or are psychoactive substances (psylocibine, bufotenin).
Tropane alkaloids are an important class of structurally related compounds having in common the azabicyclo[3.2.1]octane-3-ol skeleton, with usually are estrified with various organic acids: (-)-S-tropic, apotropic, cinnamic, tiglic, angelic, isovaleric and α-truxillic.
Tropane alkaloids mainly occurs in Solanacae, Erythroxylacae and Convolvulacae plant families, but they occur also sporadically in a number of other families e.g. Proteaceae, Rhizophoraceae plants. Genuses Atropa, Datura, Duboisia, Hyoscyamus and Scopolia
are regarded as rich sources of tropane alkaloids. The principal alkaloids of medicinal interest in this group are scopolamine and hyoscyamine which are anticholinergic agents in parasympathetic nervous system and they are used as mydriatics and spasmolytics.
Phenethylamine alkaloid group is derived biosynthetically from the amino acids tyrosine and phenylalanine. Alkaloids belonging to phenethylamine derivatives constitute an important class of natural products due to their structural similarity to many neurotransmitters. Alkaloids from the group act as stimulants (ephedrine) or hallucinogens (mescaline). Ephedra alkaloids are generally not used alone, but rather as part of herbal formulas, and are known to induce pharmacological effects beyond their sympathomimetic activities such as anti-inflammatory, anti-anaphylactic, anti-microbial, anti-histaminic, and hypoglycemic effects. Ergot alkaloids are secondary metabolites produced by fungi of the species Claviceps. Toxic effects after consumption of contaminated grains have been described since mediaeval times. Colchicine is currently being investigated for potential use as an anti-cancer drug.
Isoquinoline alkaloids, biogenetically derived from tyrosine, represent a manifold class of alkaloids within the plant kingdom. Isoquinoline alkaloids are spread mainly in the Papaverales, Rutales, Ranunculales, Geraniales, Plumboginales, Myrtiflore and Rosales species. Among them benzylisoquinoline alkaloids form an important group with different potent pharmacological activity, including analgesic compounds of morphine, antitussives of codeine and noscapine and anti-infective agents of berberine, palmatine, and magnoflorine. Papaverine serves as muscle relaxant. Thebain is worked up by pharmaceuthical industry to produce semi synthetic compounds such as the analgesic oxycodone and the opiate antagonists naloxone and naltrexone. Opium containing isoquinoline alkaloids: morphine, codeine, noscapine, papaverine, tebaine, laudanozine, retykuline has strong narcotic properties and demonstrates analgesic, spasmolytic, antitussive and obstructive properties.
Quinoline alkaloids are based on a bicyclic system in with benzene and a pyridine ring are fused together. Most of them occur in the plant family Rutaceae, especially rute. Quinoline alkaloids have also been identified in members of Malvaceae, Acanthaceae, Saxifragaceae and Zygophyllaceae families. Cinchonidine and quinine from the bark of the cinchona tree (Cinchona officinalis) are well known for their antimalarial properties.
The structures of pyridine alkaloids contain a pyridine ring together with a pyrrolidine ring (in nicotine) or a piperidine unit (in anabasine), the latter rings arising
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from ornithine and lysine respectively. The alkaloids are naturally occurring in the solanaceous family. Nicotine, the main alkaloid in the group, in small doses can act as a respiratory stimulant, though in larger doses it causes respiratory depression. Nicotine is being used by former smokers who wish to stop the habit.
Imidazole alkaloids of pilocarpine type are derived biosynthetically from histidine. Pilocarpine has the muscarinic actions of acetylcholine. It is used as a miotic in the treatment of the open-angle glaucoma.
The xanthine alkaloids are a widely used group of alkaloids as they are constituents of popular daily beverages such as tea and coffee. These alkaloids stimulate the central nervous system, respiratory system, muscles and heart. They have also therapeutic properties such as acting as an analgesic, diuretic, or bronchodilator.
Pyrrolizidine alkaloids are derived biosynthetically from the amino acid ornithine. They are spread in the Boraginaceae, Fabaceae and Composite plant families. Their toxicity has drawn a lot of attention.
Diterpene alkaloids have a diterpene skeletal structure. The group of alkaloids comprises highly toxic compounds: aconitine, mesaconitine and hypaconitine. The toxicology of these alkaloids derives from activation of the sodium channel of excitable cell membranes leading to rapid paralysis of cardiac, muscular and neural tissues.
3. Sample preparationSample preparation is the crucial first part in a natural product analysis because it is necessary to extract the desired chemical components from the material, dissolve the analyte in a suitable solvent and remove as many interfering compounds as possible from the solution. Application of chromatographic techniques, especially HPLC, requires preliminary sample preparation providing a sample free of components that may deteriorate the column. Various methods of extraction are used for isolation of different alkaloids from plant material, pharmaceutical formulations and biological samples. In the extraction and isolation of alkaloids one has to consider that alkaloids usually occur in plants as salts of organic or inorganic acids, sometimes exist as tannin complexes, and often together with non-alkaloidal compounds. The procedure of extraction depends on the class of alkaloids and ballast substances coexisting with the alkaloidal fraction. Natural samples with a high concentration of nonpolar compounds (e.g. lipids) should preferably be extracted with water containing acids to obtain the alkaloids in aqueous solution as
salts. Samples containing a large number of water soluble compounds (e.g. phenols, tannines) should be extracted with organic solvents immiscible with water after addition of alkali to obtain the alkaloids in the organic solvent as free bases.
3.1. Indole alkaloidsVarious methods are used for extraction of indole alkaloids from plant material. Generally in liquid-solid systems acidic extractants are used. The following mixtures of solvents were used: MeOH with HCl (5%) [5], or 2% [6], MeOH with 1% CH3COOH [7], H2O with TFA (0.1%) [8], n-hexane with 1% HCl [9], MeOH/H2O with HCl (1%) [10], 2-propanol/H2O with lactic acid (1%) [11], MeCN/H2O with 1% CH3COOH [12], water with 10% acetic acid [13], water with 2% sulfuric acid [14].
The extraction of indole alkaloids was performed also without addition of acids, for example extraction with pure MeOH [15-17], EtOH [18-21], dichloromethane [15], acetone [15] or MeOH/H2O [23] was reported. Sometimes extraction was performed in extractant at basic pH, e.g. MeOH/H2O with addition of ammonia [24], EtOH with ammonia [25]. The MeOH extract was acidified with 10% acetic acid to pH 2.8, and then dissolved in water. The aqueous solution was extracted with CH2Cl2, while the aqueous solution was made alkaline with 25% ammonia to pH 8.5, and extracted again with CH2Cl2 [26]. Ergot alkaloids from rye flour or grounded rye were extracted by adding 100 mL of dichloromethane/ethylacetate/methanol/ammonia (25%), (50/25/5/1, v/v/v/v) [1].
The macrolactam-type indole alkaloids from Ipomoea obscura were extracted with methanol. The solvent was evaporated under reduced pressure at 40°C, the residue re-dissolved in 2% aq. tartaric acid and extracted with ethyl acetate. After evaporation of the organic solvent, the residue was dissolved with methanol [27]. Another procedure of extraction of terpenoid indole alkaloids from Catharanthus pusillus was applied. The plant material was mixed with absolute ethanol, homogenised, centrifuged and the ethanolic extract was transferred into a round bottom flask. The pellet was re-extracted in a similar fashion and the combined ethanolic phases concentrated to dryness under reduced pressure. For the extraction of vindoline, the plant material was mixed with buffer (composed with glycine, NaCl and NaOH) at pH 10 and dichloromethane. The mixture was homogenized and centrifuged. The organic liquid phase was taken and transferred to a round bottom flask. The slurry was extracted again by addition of dichloromethane [28].
SPE method involves selective extraction of the analytes from liquid samples onto solid support of different varieties and types (e.g. silica gel, alumina,
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florisil, kieselguhr, reversed-phase sorbents such as: octyl, octadecyl, diol, cyano, amino, ion-exchange sorbents). The sample is directly passed through previously conditioned cartridges filled with a given sorbent and analytes are directly collected, whereas co-extractives are retained on the sorbent. It can be performed another way in which a sample is applied in solvent of low elution strength. The analytes adsorbed are eluted with solvent of higher elution power. Extraction of indole alkaloids from Rauwolfia serpentina tissue was performed on SCX cation-exchanger [29]. Tissues were extracted with methanol. After filtering, the extract was evaporated to dryness. Extract was dissolved in methanol and acidified with 0.1 M HCl. Acidified solution was extracted with SCX cation –exchanger.
3.2. Tropane alkaloidsDue to thermal instability and sensitivity to strong acidic and basis conditions of tropane alkaloids the method of solid-liquid extraction should be carefully selected. The first step of extraction should be with diluted acids like 5% HCl, 5-10% acetic acid or 0.01% H2SO4 [30-32]. Jia et al. [33] found the extraction of Datura alkaloids the most efficient at pH 2-3. When alkaloid free bases are to be extracted, alkaline organic phases are used. Fliniaux et al. compared the efficiencies of both acidic and alkaline solutions for the extraction of tropane alkaloids from plant material. They used: 0.2 M sulphuric acid, methanol-0.1 M HCl (24:1, v/v), methanol-27% ammonia (24:1, v/v), methanol-chloroform-27% ammonia (24:1, v/v) [34]. Similar results were obtained by all procedures.
Kintz et al. have extracted of scopolamine from children hairs. After liquid–liquid extraction with 5 mL of a mixture of methylene chloride/isopropanol/n-heptane (50/17/33, v/v/v) and evaporation of the organic phase to dryness, the residue was reconstituted in 100 μL of methanol.
Mroczek et al. [35] analysed the content of l-hyoscyamine and scopolamine extracted from thorn apple’s leaves. When 1% tartaric acid in methanol was used at 90 ± 5oC on heating mantle for 15 min, the highest amounts of scopolamine were measured also in comparison to more sophisticated methods such as UAE (ultrasound assisted extraction) or PLE (pressurised liquid extraction). However, the amounts of l-hyoscyamine were comparable to USE at 60oC and lower than PLE procedures.
For cocaine and benzoylecgonine extraction from coca leaves, microwave-assisted extraction (FMAE) was optimised with respect to the nature of the extracting solvent, the particle size distribution, the moisture of the sample, the applied microwave power and radiation time [36]. FMAE generated extracts similar to those
obtained by conventional solid-liquid extraction but in a more efficient manner.
The pressurized liquid extraction (PLE) was used for cocaine and benzoylecgonine extraction from coca leaves [37]. Mroczek et al. optimized PLE conditions for extraction of l-hyoscyamine and scopolamine from thorn apple leaves [35].
El-Shazly et al. [38] applied SELLP procedure for isolation of pure alkaloidal fractions from Hyoscyamus sp. The basified aqueous extract was applied into dry ExtrelutTM column, and the liquid was completely absorbed by the kieselguhr. Tropane alkaloids free bases which are exposed on the surface of the kieselguhr particles are eluted by organic solvents such as chloroform.
In some cases liquid-liquid extraction were used for isolation of tropane alkaloids. At first the acidic extract is extracted with chloroform in a separation funnel to remove acidic co-extractives. Then the remaining extract is alkalized with ammonia solution to pH about 9-9.5 and extracted with non-polar organic solvents such as chloroform, benzene, toluene, or dichloromethane [39,40].
SPE of tropane alkaloids was usually performed on RP-18 columns. The procedure was applied for plant extracts, blood serum, urine and egg yolk samples [41-43].
Keiner and Dräger [44] applied cation-exchange SPE for isolation of calystegines from plant samples, where they were retained by charge of the secondary amino group.
3.3. Isoquinoline alkaloidsVarious methods are used for extraction of isoquinoline alkaloids from different natural samples. Usually simple techniques of extraction were applied. It was maceration or percolation at room temperature with aqueous extractants or alcohols [45-48]. For liquid-solid extraction of isoquinoline alkaloids, aqueous acidic solutions were often applied [49,50]. Acidified methanol or ethanol with HCl or H2SO4 was also used [51,52]. Sometimes organic solvents are used for extraction such as methanol and dichloromethane, methanol and chloroform or dichloromethane [53-55]. The extraction was often assisted by shaking or ultrasonification [56-58].
3.4. Phenylethylamine alkaloidsThe following procedure was used for isolation of phenylethylamine alakloids from Colchicum crocifolium. Dried plant material was extracted with MeOH in a Soxhhlet apparatus for 3 h. The solvent was evaporated under reduced pressure to yield a MeOH-extract, which
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was fractionated [59]. Briefly, the MeOH-extract was dissolved in 5% acetic acid and extracted with light petroleum, after which the aqueous acid residue was re-extracted three times with diethyl ether. The acidic aqueous residues were made alkaline (pH 9) with 10% NH4OH followed by extraction three times with CH2Cl2. The aqueous residues were then adjusted to pH 12 with 10% NaOH, and then extracted three times with diethyl ether and finally three times with CH2Cl2.
A sonification extraction was usually used for separation of ephedrine alkaloids. The sonification and microwave extraction were used for isolation of ephedrine alkaloids from Ephedra natural products [60]. Sonification was performed by use solvent containing methanol or a mixture of hydrochloric acid and methanol (0.8:99.2, v/v)) at different temperatures (room temperature, 40 or 50oC) for 15 min. Regarding microwave extraction, a weighed amount of ground sample (0.25 g of E. vulgaris aerial parts) was extracted with 5mL of solvent (methanol or a mixture of hydrochloric acid methanol (0.8:99.2, v/v)) by using a monomode microwave apparatus with a closed vessel system and subjected to different temperatures for different times of irradiation (40oC for 15 min or 60oC for 4 min or 80oC for 1 min). The comparison between sonication and microwave extractions indicated that sonication was the most efficient procedure, allowing the highest yield of all considered analytes in a short time.
3.5. Quinoline derivativesThe extraction of major alkaloids from Cinchona bark is usually performed after preliminary pulverizing, grinding, sieving and drying of the bark at 110oC followed by treatment with alkali and Soxhlet extraction in hot toluene [61], benzene or methanol [62].
Quinine and quinidine are extracted from plasma or urine also by making the sample basic with, for instance sodium or aqueous ammonia, and extracting into an organic solvent such as dichloromethane or diethyl ether [63,64].
For determination of quinine in plasma, samples were subjected to protein precipitation with acetonitrile. The mixture was finally centrifuged at 4oC for 10 min. The supernatant was transferred into a polypropylene tube and evaporated to dryness under nitrogen at room temperature. The solid residue was reconstituted in MeOH/ammonium formate 20 mM 1:1 adjusted to pH 4.0 with formic acid, vortex-mixed and centrifuged again [65].
3.6. Pyridine and piperidine alkaloidsNicotine and cotinine were extracted from rat plasma [66]. Plasma was added to a centrifuge tube containing
2-phenylimidizole, 5% antifoam/phenol red solution, 30% ammonia, and dichloroethane and mixed by gentle inversion for 1 min. The solution was centrifuged 15 min using a Microfuge. The supernatant was discarded and the clear bottom layer was placed into a tube and dried under N2 gas. The sample was reconstituted with HPLC buffer (30 mM citric acid, 30 mM KH2PO4, 3.65 g L-1 triethylamine, 0.6 g L-1 1-heptanesulfonic acid, 90 mL L-1 acetonitrile, pH 4.8) was added.
Hair samples containing tobacco alkaloids were washed three times with 3.0 mL of dichloromethane by vortex-mixing. After drying, the samples were digested with 1.0 mol L-1 NaOH for 14 h at 50oC and then centrifuged. Afterwards, the clear supernatant was diluted with an equal volume of a buffer of ammonium acetate + ammonia (pH 10.0) [67].
In another procedure serum samples containing nicotine and its metabolites were prepared by SPE method [68]. Serum sample was added to internal standard solution, water and 25% (w/v) trichloroacetic acid to remove proteins. The solutions were centrifuged at 10,000 g for 5 min after vortexing. The supernatant was applied to SPE cartridges. An Oasis MCX cartridge (Waters) was conditioned with 1mL of methanol and 1 mL of water. Serum samples were loaded and allowed to flow by gravity. Cartridges were washed with 1 mL water and 1 mL methanol, and dried for 5 min. Analytes were eluted with freshly prepared 1 mL methanol with 1% ammonia (v/v). Eluates were evaporated to dryness under a nitrogen stream at 50°C. Samples were reconstituted in acetonitrile with 0.1% formic acid (v/v).
The acidified plasma supernatant and urine containing nicotine and its metabolites were then subjected to solid-phase extraction (SPE) using a combination of Oasis HLB and Oasis MCX mixed mode cartridges [69]. The SPE cartridges for both plasma and urine were conditioned with methanol followed by 10% aqueous trichloroacetic acid for plasma and 5 mM aqueous ammonium formate (pH 2.5) for urine. The samples were loaded onto the cartridges and the target analytes were subsequently eluted with 2 mL methanol containing 5% concentrated aqueous ammonium hydroxide (v/v). 1% concentrated aqueous hydrochloric acid in methanol (v/v) was added prior to evaporation of the eluent. Extracts were evaporated to dryness and residues were reconstituted in initial mobile phase conditions.
SPE procedure was also used for extraction of tobacco alkaloids [70]. SPE column was pre-washed with methylene chloride, methanol, and finally with water. After the acidified sample was loaded onto the column, the column was washed with acetic acid and dried under positive pressure N2. The column was then washed with
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hexane and then of hexane-ethyl acetate (1:1), followed by methanol. After washing, the analytes were slowly eluted with 2×3 mL of methylene chloride/isopropanol/ammonium hydroxide (78:20:2). The final extract was dried in the vacuum evaporator without heat, and the residue was reconstituted in methanol with 0.1% formic acid for the analysis.
Piperine analogues were extracted from plasma by SPE [71]. The various steps involved in the recovery procedure were: (a) conditioning of SPE cartridge C18 with 1.0 mL methanol, followed by 1.0 mL water, (b) loading of diluted (1:4, v/v) plasma samples (1.0 mL) onto cartridge and drying under positive pressure, and (c) samples were washed with 2 mL of water followed by elution with 2 mL of methanol.
3.7. Imidazole alkaloidsArecoline alkaloids were prepared from cord serum, or urine with 10 internal standards and NH4Cl saturated solution at pH 9.5 added, were transferred to a screw-capped glass tube with chloroform/isopropanol (95:5, v/v) [72]. The tubes were placed in a horizontal shaker for 5 min. After centrifugation, the organic layer was transferred to another screw-capped glass tube, and back-extracted with 0.5M HCl for 5 min. After centrifugation, the acidic layer was neutralized with NaOH, or ammonia solution. Re-extraction with chloroform/isopropanol (95:5, v/v) was finally conducted for 10 min. The organic phase was evaporated to dryness under a stream of nitrogen at 40°C. The dried residue was dissolved in 10 mM ammonium acetate (pH 4.3) solution.
Alakloids from Pilocarpus sp. Were extracted with 10% ammonia; after 15 min extraction is carried out 3 times with CHCl3; the pooled organic extracts are re-extracted twice with 2% H2SO4; the pooled acid extracts are adjusted to pH 12 with NH4OH and extracted twice with CHCl3 [73].
3.8. Xanthine alkaloidsCaffeine from traditional Chinese medicinal prescriptions which contain Theae folium was extracted by SPE [74]. In the procedure, the SPE C18 cartridges were washed with water and then dichloromethane was used to elute the compounds. The eluate was collected and concentrated under reduced pressure to dryness. Finally, the residue was dissolved in 50% methanol.
The sequential extraction of samples containing caffeine was applied [75]. First samples with 50% methanol, than with 75% methanol, and finally with 100% methanol for 20 min at 60°C were extracted. After each extraction step, the sample was centrifuged at 10°C for 10 min and the supernatant collected and the solid
submitted to the following extraction step. Extractions were carried out on a multi-frequency ultrasonic bath operating at 25 kHz at 100% intensity output. After the last extraction, supernatants were combined and brought up with water and an aliquot was collected, which was filtered through 0.2-m nylon syringe filter before the HPLC analysis.
3.9. Pyrrolizidine alkaloidsIsolation of pyrrolizidine alkaloids was obtained by SPE using C18 cartridges [76].
For extraction of pyrrolizidine alkaloids from Boraginaceae species, the plant organs or cultured roots were washed with tap water, dabbed dry, weighed, and ground in a mortar with liquid nitrogen and sea sand before they were extracted twice for 30 min with methanol containing 1% HCl (25%) and centrifuged [77]. The supernatant of the combined methanol extracts was evaporated. The resulting residue was dissolved in methanol.
In another procedure, the sample preparation internal standard was added to serum and mixed well before being deproteinized with 6% HClO4 (v/v) [78]. Then KH2PO4–KOH (1 M; pH 8.1) was added. The mixture was vortex mixed and centrifuged. The supernatant was applied to a C18 solid phase extraction (SPE) cartridge which had been conditioned with methanol followed by water. Each cartridge was then washed with water and 1% ammoniated methanol (v/v). They were evaporated to dryness under a flow of nitrogen in a heating block at 40°C. The residue was dissolved by initial mobile phase.
3.10. Quinolizidine alkaloidsAlkaloid extraction procedure was proposed by Wink et al. [79]. According to this method, plant material was homogenized in 0.5 M HCl. After 30 min at room temperature, the homogenate was centrifuged for 10 min at 10 000 x g. The supernatant was made alkaline by adding ammonia or 2 M NaOH and was applied to Extrelut columns. Alkaloids were eluted with CH2Cl2 and the solvent evaporated in vacuo.
Liu et al. used SPE for extraction of quinolizidine alkaloids from dog plasma [80]. The sample was vortexed for 30 s and extracted with OASIS HLB Extraction Cartridges under reduced pressure. Activation of the cartridges was achieved by sequential washing with methanol and distilled water. The cartridges loaded with the samples were firstly washed with 2% acetonitrile solution and then were eluted with acetonitrile. The eluate was reduced to dryness using a centrifugal vacuum concentrator. The residue was reconstituted in mobile phase.
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4. Thin layer chromatography (TLC)TLC is a chromatographic method widely used for qualitative rather than quantitative analysis of alkaloids, isolation of individual substances from multicomponent mixtures, and preparative-scale isolation. TLC provides a chromatographic plant extract and drug fingerprint. Multiple samples can be analyzed at the same time on a single TLC plate, reducing the time of analysis and solvent volume used per sample. TLC with densitometry is the method most frequently applied for quantitative analysis of biological samples, e.g. plant extracts. Advances in instrumental high-performance thin-layer chromatography (HPTLC) have resulted in increasing application of planar chromatography in quantitative analysis. The possibility of separation of components present in a mixture and the simultaneous handling of a large number of samples has led to extensive use of HPTLC for analysis of natural samples. TLC is the easiest technique with which multidimensional separations can be performed. Particularly valuable separation results can be achieved when using various stationary and mobile phase systems as an advantage over different separation mechanism. TLC coupled with densitometry can be used for quantitative analysis of investigated compounds. TLC also was often used for preparative isolation of alkaloids, purification of multicomponent samples and control of the separation efficiency of the different chromatographic methods. Nowadays, HPTLC is a routine analytical technique.
Most TLC procedures for analysis of indole alkaloids use an adsorbent stationary phase such as silica gel, often with fluorescence agent added, since all indole alkaloids adsorb UV light and mobile phase containing strongly polar modifier (methanol, ethanol), medium or weakly polar diluent (toluene) and addition of basic compounds such as ammonia. Clavine and ergoline alkaloids were identified on silica gel as stationary phase and in chloroform (CHCl3), methanol (MeOH), ammonia mixture or ethyl acetate (AcOEt), MeOH, H2O, dimethyloformamide (DMF) as mobile phases [81]. TLC separation of monoterpenoid oxindole alkaloids was achieved on silica gel with CHCl3 and acetone mixture as eluent [82]. Two indole alkaloids, 12-methoxykopsine and danuphylline B, were obtained from the leaf extract of the Malayan Kopsia species, K. arborea, and isolated on silica plates by centrifugal TLC method with mobile phases containing: CHCl3/MeOH, AcOEt/Hexane, or diethyl ether (Et2O)/hexane/ammonia [83]. Fractions of Alstonia angustiloba plant extract, containing indole alkaloids, were re-chromatographed by centrifugal TLC using different nonaqueous eluent systems [84].
Centrifugal TLC (silica, MeOH/CHCl3 or AcOEt/hexane/ammonia) was successfully applied for isolation of alkaloids from Kopsia species [85]. Subramaniam et al. have analyzed monoterpenoid indole alkaloids from Kopsia singapurensis by centrifugal TLC by use different mobile systems [86]. Monoterpenoid indole alkaloids in Catharanthus roseus extract are separated by TLC (on silica plates and eluent containing: ethanol (EtOH), CHCl3, ammonia) and identified based on their Rf values, as well as on their chromogenic reaction to ceric ammonium sulfate spray reagent [87]. TLC was applied for micropreparative isolation of indole alkaloids from Rauvolfia yunnanensis [88]. The authors used preparative silica plates and a mixture of AcOEt, MeOH and diethylamine (DEA) as mobile phase. Micropreparative TLC was used for isolation of ervatamine-type indole alkaloids from Ervatamia officinalis in system: silica gel as adsorbent and CHCl3/MeOH as eluent. TLC method was applied to purification of isolated alkaloids on silica plates in eluent systems: CHCl3/MeOH or petroleum ether/AcOEt/DEA [89]. On preparative silica gel plates with mixtures of MeOH and dichloromethane or CHCl3 and AcOEt/hexane fractions of plant extract from Strychnos cathayensis were purified [90]. For isolation of henricinols (indole alkaloids obtained from Melodinus henryi) silica preparative plates and mixture of AcOEt and CHCl3 was used [91]. The alkaloidal fraction obtained from Tabernaemontana catharinensis was analyzed on silica plates by use mixture of MeOH and CHCl3 [92]. Isolated alkaloids were identified by UV-ViS or IR spectra. Silica gel plates were applied for purification of indole alkaloidal fraction obtained from leaf extracts of Rauvolfia bahiensis [93]. The alkaloidal extract of Vinca herbacea was purified by preparative TLC on neutral Al2O3 in toluene/AcOEt/DEA solvent system [26]. Two curarizing quaternary indole alkaloids from Strychnos quianensis were analyzed on silica gel plates in eluent system containing MeOH, Me2CO and MeCOONa [94]. Purification of extract from Strychnos moandaensis was performed on preparative silica gel plates in mixtures of MeOH/CHCl3 as eluent [95]. For isolation of antileishmanial active indole alkaloids from Aspidosperma ramiflorum preparative silica gel plates and mixtures of MeOH/CHCl3 or CHCl3/AcOEt/MeOH/triethylamine were applied [96]. For separation of indole alkaloids by TLC, gradient elution was successfully used. Components of plant extract from Cicer arietinum were separated on silica gel in eluent gradient system containing CHCl3/MeOH/H2O with increasing polarity [97]. Gradient TLC elution was used for separation of monoterpene indole alkaloids from Psychotria stachyoides [98]. Mixtures containing
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CH2Cl2/MeOH/NH4OH as eluent with increasing polarity were applied. Aspidosperma and Hunteria type indole alkaloids were separated on silica gel with AcOEt/hexane [99]. Lundurines, cytotoxic indole alkaloids from Kopsia tenuis, were isolated initially by column chromatography, followed by re-chromatography using centrifugal TLC with mixtures: Et2O/hexane, Et2O/MeOH, CHCl3/MeOH as eluents [100]. Centrifugal TLC method was used for re-chromatography of partially resolved fractions containing macroline indole alkaloids from Alstonia angustifolia [101]. Solvent systems used for separation of the alkaloids were mixtures containing MeOH, EtO2, CHCl3, and hexane saturated NH3. Fractions of Ambelania occidentalis plant extract were purified on preparative silica gel plates using AcOEt/CHCl3 or MeOH/CHCl3 [102]. Monoterpenoid indole alkaloids from Catharanthus roseus plant extract were separated on silica gel with various solvent systems and the radioactivity was visualized and quantified by exposure of the TLC to a storage phosphor screen [103]. Mixtures of CH2Cl2 with MeOH, acetone or hexane were applied as eluents on silica gel for separation of indolo[2,3a]quinolizine alkaloids [104]. Indole alkaloids from Kopsia arborea were initially isolated by column chromatography followed by re-chromatography of partially resolved fractions using centrifugal TLC in solvent systems containing Et2O/hexane or AcOEt/hexane saturated NH3 [105]. Indole alkaloids from different cyanobacteria were isolated on preparative silica gel plates with mobile phase containing AcOEt/MeOH/H2O [106]. The quantification of yochimbine in Pausinystalia yochimbe was performed on silica HPTLC plates with mixture of toluene/AcOEt/DEA [107]. Thoden et al. proposed the use of centrifugal TLC for fractionation of Crotalaria species plant extracts containing pirolizidine alkaloids [108]. As eluent mixtures of MeOH and CH2Cl2 and silica gel plates were used.
Silica gel plates and nonaqueous eluents were commonly used for analysis of tropane alkaloids. Dimeric tropane alkaloids were analyzed in normal phase system containing silica gel as stationary phase and mixture of MeOH/CHCl3 as mobile phase [109]. On silica gel plates tropane alkaloids from Merremia genus plant extracts in eluent containing CHCl3/MeOH/ammonia were isolated [110]. TLC separation of alkaloids from Schizanthus litoralis was performed on silica gel with mixtures of CHCl3/Me2CO or CHCl3/ Me2CO/ammonia and on aluminum oxide with Et2O/EtOH [111]. Brachet et al. described separation of tropane alkaloids from Erythroxylum lucidum on silica gel with use of Me2CO/ammonia and on aluminum oxide using Et2O/EtOH [112]. TLC on silica gel plates and eluents containing MeOH/CHCl3/ammonia have
been employed for the analysis of alkaloid extracts from Hyoscyamus niger [113], Solanum tuberosum [114], Ceropegia juncea [115] and Erythroxylum emarginatum [116]. Bringmann et al. have separated alkaloids from Erythroxylum zeylanicum plant extract using preparative silica gel plates and eluents containing, e.g. MeOH/CH2Cl2, MeOH/AcOEt/ammonia, and MeOH/CHCl3/water [117]. The procedure of separation and quantification of tropane alkaloids from Datura species by TLC has been described by Mroczek et al. [118]. Alkaloids were separated on silica gel HPTLC plates with two mobile phase systems: acetone/MeOH/water/ammonia and MeCN/MeOH/HCOOH. Fig. 1 presents densitograms of the plates obtained for separation of mixture of alkaloid standards and Datura fastuosa plant extract. The authors compared quantitative results for investigated alkaloids obtained by HPLC and HPTLC and received good correlation between both methods. Singh et al. proposed a TLC densitometric method for the determination of scopolamine in chromatographic system: silica gel HPTLC plates and aqueous mobile phase - acetone/MeOH/water/ammonia [119].
TLC of mescaline was carried out on silica gel plates in the eluent system: CHCl3/BuOH/ammonia [120]. Fast determination of colchicine from pharmaceuticals and vegetal extracts was performed by TLC-densitometry [121]. The extract was separated on silica gel layers with a mixture of acetone/CHCl3/DEA as a mobile phase. HPTLC determination of colchicine in a pharmaceutical formulation has been reported [122]. Analysis was performed on silica gel plates with MeCN/AcOEt/water /HCOOH. Ephedra alkaloids from Sida species were determined on nano silica HPTLC plates with toluene/AcOEt/DEA as eluent [123].
Opium alkaloids were chromatographed on silica gel plates with nonaqueous eluent containing toluene/acetone/EtOH/ammonia [124]. Samples containing alkaloids were analyzed by TLC, subsequently by HPLC and additionally identified by MS (Fig. 2).
Piperine was determined on silica plates by use of petroleum ether, CH2Cl2 and HCOOH [125]. The plates were saturated in eluent vapors for 20 minutes before developing of chromatograms.
A simple spectrophotometric-TLC method was used for determination of colchicine in Colchicum species [126]. Analysis was performed on silica gel plates with eluent consisting with acetone/CH2Cl2/DEA. Ellington et al. have separated colchicine from genus Androcybium on preparative silica gel plates with MeOH/CH2Cl2 in an ammonium-saturated atmosphere [127].
In TLC especially on plates with polar bonded phases (CN-, Diol-, and NH2-silica), two-dimensional separations can be realized using NP adsorption
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systems with non-aqueous eluents and RP partition systems with aqueous eluents, which allows for better or full separation of complex mixtures. The method can be applied during the analysis of complex plant mixtures and allows selected compounds to be identified by retention coefficients in two directions. The application of the most selective systems in 2D-TLC separation of standards’ mixture of isoquinoline alkaloids and alkaloid extracts from herb of Fumaria officinalis is presented in Fig. 3 [128].
Special modes of developing a TLC chromatogram such as automated multiple development (AMD) were also used for analysis of alkaloids. AMD is an instrumental technique of planar chromatography which uses an eluent gradient starting from the most polar to the least polar. The migration is performed by successive steps and at each new development the proportions of the eluent constituents change; so the polarity is decreasing when the distance increases. Gradient development with a linear eluotropic profile leads to a band re-concentration improving the separation. A successful separation depends mainly on the choice of the solvent components and optimization of the shape of the gradient. The stepwise movement of the elution front and the repeated developments increase the resolution. AMD has proved to be an efficient planar chromatographic technique that provides increased separation for compounds with neighboring structures. Pothier and Galand applied AMD for separation of opium alkaloids by using different solvents as eluents (Fig. 4) [129].
(a)
(b)
Figure 1. HPTLC-densitometric assay of the mixture of (1a) scopolamine–N-oxide (Sk–NO), scopolamine–N-methyl bromide (Sk-Me), l-hyoscyamine (H) and scopolamine (Sk). Stationary phase: silica gel 60 F254 HPTLC plates, 20×10 cm, 0.25 mm thickness; mobile phase: (a) acetone–methanol–water–25% ammonia (82:5:5:8, v/v), then after evaporation of the solvents; (b) acetonitrile–methanol–85% formic acid (120:5:5, v/v). Scan was recorded at 205 nm [35]; and (1b) of l-hyoscyamine (H) and scopolamine (Sk) in the extract from seeds of Datura fastuosa purified by SPE procedure. Details as in Fig. 1a [35].
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Over Pressured Layer Chromatography (OPLC) is nearly equivalent to HPLC. It is a planar chromatographic method using a pressured chamber in which the vapor phase above the sorbent is practically eliminated. The eluent is pushed through the sorbent layer and continuous development can be performed by a pump. The method was applied by Mincsovics for separation of xanthine alkaloids in black tea [130]. The separation was performed on silica layer with eluent containing toluene and CH3COOH. Fig. 5 presents schematic diagram of bilateral band compression – the method used in this study. Bilateral band compression has been used to increase the sensitivity of detection of minor components of a mixture.
Recently, TLC method was conducted with mass spectrometry (MS). The TLC/MS combination has the potential to provide low-level, highly specific detection of targeted compounds and molecular mass and structure determinations for unknowns. TLC/MS has been employed for the analysis of xanthine alkaloids. Caffeine was analyzed in Ilex vomitoria extract on C18 plates with mixture of MeOH and water as mobile phase by TLC/MS [131]. Aranda and Morlock described determination of caffeine in pharmaceuticals and energy drink samples by TLC coupled with MS [132]. Schematic diagram of the interface components is presented in Fig. 6. Analysis was performed on silica gel plates with eluents containing MeOH/formate buffer at pH 4.0. The TLC/MS was also applied for determination of caffeine, codeine and ephedrine on C18 plates and eluent consisting with MeOH and water [133].
Shariatgorj et al. have applied thin-layer chromatography/laser desorption ionization mass spectrometry for facile separation and identification of quaternary protoberberine alkaloids from Berberis barandana [134]. The silica gel TLC plates were developed with buthanol, water and CH3COOH.
A further field of application of TLC is the purification of chromatographic fractions. Tood et al. described separation of tropane alkaloids from Convolvulus arvensis on preparative silica gel plates using eluent consisting with MeOH/CHCl3/water/ammonia [135]. The extract from Datura stramonium was chromatographed on preparative TLC silica gel plates [136]. Alkaloids were eluted with mixture of CHCl3/DEA. The alkaloidal fractions from Erythroxylum species were separated on preparative silica gel plates in eluent system containing MeOH/CHCl3 [137]. Mixture of MeOH/CHCl3/ammonia was applied on silica gel preparative plates for purification of Mandragora officinarum plant extract [138].
Table 1 covers some selected TLC methods for analysis of alkaloids from different classes.
5. High Performance Liquid Chromatography (HPLC)In recent years there has been a remarkable development in the format of the chromatographic columns and stationary phases, as well as highly specialized organization of HPLC components. Currently HPLC is the most versatile and most widely applied technique in the analysis of natural products including alkaloids. In most cases, compounds are detected with ultraviolet (UV) detectors or photodiode array detectors (DAD). Sophisticated coupled techniques like HPLC-mass spectrometry (LC-MS) and HPLC-molecular magnetic resonance (HPLC-NMR) are increasingly used in the analysis of alkaloids. HPLC is also useful for quantification of alkaloids for pharmacokinetic studies.
5.1. Normal-phase LCNP-HPLC is rarely applied in separation of alkaloids. However, the use of these systems for the analysis of alkaloids is sometimes reported. Usually silica column and strongly polar modifier (acetonitrile) and medium polar diluent (dichloromethane) are used for these purposes. For the analysis of indole alkaloids from Haraldiophyllum species, a chromatographic system containing cyanopropyl stationary phase and mixture of 2-propanol/hexane as mobile phase was used [148].
Rarely, for analysis of alkaloids, silica stationary phase coated with metal ions was used. Piperine isomers were separated on a silver-modified cation-exchange ligand-covered silica material as stationary phase with eluent system containing MeCN/iPrOH/hexane [149].
5.2. Reversed-phase LCThe optimization of alkaloids’ analysis in RP systems consists in reducing of ion-exchange interactions between basic analytes and residual surface silanols. There are several methods to achieve the reduction of the ionic interactions such as: using a mobile phase at low pH (suppression of silanols’ ionization); using a mobile phase at high pH (suppression of alkaloids’ ionisation); addition of ion-pairing reagent to mobile phase (formation of non-polar, non-charged ion-pairs with analyte); addition of relative strong bases to eluent playing the role of silanol blockers and/or alkaloids ionization suppressants; selecting a stationary phase.
Some alkaloids were separated in RP system with eluents containing only organic modifier and water. The ergot alkaloids, fungal secondary metabolites of significant toxicological and pharmacological activities, were successfully analysed on C18 stationary phase with a gradient of 20-70% MeCN in water [150]. The
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analyses of alkaloids from Psychotria leiocarpa were carried out using C18 column and mixture of MeOH /water as eluent [151]. The eluent containing only MeOH and water was applied for separation of indole and carbazole alkaloids in Glycosmis montana plant extract [152] and from Alstonia scholaris [153].
Xanthine alkaloids were often successfully analysed on RP columns in simple eluent systems containing only organic modifier and water. Caffeine, theophylline and theobromine were determined in food samples by HPLC in eluent system containing MeCN and water [154-156] or MeOH and water [157-159]. The use of a monolithic column provided excellent and rapid separation of caffeine from the endogenous sample components and from structurally similar compounds in less than a minute [160].
Rarely, indole alkaloids were chromatographed in eluent system containing buffer at neutral pH. Mixture of MeOH and phosphate buffer at pH 7.0 was applied for separation of oxindole alkaloids from leaves of Mitragyna inermis [161]. Tang et al. used for analysis of catharanthine and vindoline from Catharanthus roseus an eluent system containing MeCN and phosphate buffer at slightly acidic pH (6.0) [162]. Eluent system containing buffer at pH 6.5 has been employed for the analysis of colchicine in a human specimen [163]. Mobile phase containing mixture of MeOH and water was applied for determination of nicotine [164]. The addition of ammonium carbonate to the mobile phases was often used for analysis of ergot alkaloids. Separation of these compounds from Claviceps purpurea was carried on C18 column with eluent containing MeCN/water/
Figure 2. Thin layer chromatography (TLC), high-performance liquid chromatography (HPLC) and liquid chromatography/mass spectrometry (LC/MS) analyses of latex: (a) TLC of three families indicates the presence of the novel salutardine band not seen in the control. The track labeled standards includes reticuline, codamine and laudanine in order of increasing distance from the origin; (b) HPLC confirmed the novel accumulating alkaloid as salutaridine, the salutaridine peak is clearly present at just under 7.6 min retention time, and is absent in the control sample [124].
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(NH4)2CO3 [165-168]. Wang et al. have used for analysis of ergot alkaloids the mobile phase consisting of MeCN, water and CH3COONH4 [169]. Ergot alkaloids were also analysed with mobile phase containing MeCN/water/tartaric acid/ammonium chloride [170].
Quinine was determined on C18 column with eluent containing MeOH, MeCN, water and ammonium formate [171]. Ammonium acetate was added to mixture of MeOH and water for separation of nicotine and related alkaloids in human plasma [172]. The simple method should be useful for monitoring tobacco exposure, for nicotine pharmacokinetic studies, and for determining the usefulness of nicotine biomarkers, including metabolite ratios. Nicotine was also analyzed on C18 column with multicomponent eluent containing MeOH,
phosphate buffer and (NH4)2SO4 [173]. Nicotine, cotinine and related alkaloids were determined in human urine and saliva by LC-MS on C18 column with MeOH and aqueous solution of HCOONH4 [174].
Zhang et al. described LC/ESI-MS method for determination of isoquinoline alkaloids from Tinospora sagittata and Tinospora capillipes [175]. Separation of alkaloids was performed on C18 column with eluent consisting of MeOH, MeCN, water and ammonium acetate.
The mobile phase containing MeCN/water/CH3COONH4 has been employed for determination of hepatotoxic pyrrolizidine alkaloids in a medicinal plant - Symphytum officinale on C18 column by LC-MS [176]. The eluent containing addition of HCOONH4 to a
Figure 3. Videoscans of chromatogram (a) for standards of alkaloids scanned at 366 nm and 254 nm. Eluent systems: I direction: 60% MeOH in water + 2% ammonia; II direction: 10% MeOH in diisopropyl ether + 2% ammonia; and (b) of Fumaria officinalis herb extract scanned at 366 and 254 nm. Eluent systems: I direction: 60% MeOH in water + 2% ammonia; II direction: 10% MeOH in diisopropyl ether + 2% ammonia [128].
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mixture of MeOH and water was used for determination of quinolizidine alkaloids matrine and oxymatrine in rat blood and derma by LC-MS [177].
Swainsonine, a polyhydroxy alkaloid, was chromatographed by LC-MS/MS on C18 column with the mobile phase containing MeOH, water and CH3COONH4 [178].
Often, particularly in toxicological investigation, there is a need for simultaneous determination of alkaloids belonging to different chemical groups in complex matrices. Plant alkaloids from different classes in serum and urine were separated on C18 column in eluent system MeCN/phosphate buffer at pH 6.5 (Fig. 7) [179].
5.2.1. Mobile phases at acidic pHThe use of mobile phase at acidic pH by addition of appropriate buffers or acids suppresses the ionization of free silanol groups on silica surface, which reduces ion exchange mechanism of retention. In the acidic mobile phases, decreases of retention of alkaloids, more symmetrical peaks and increases in system efficiency were often obtained.
Indole alkaloids were often analysed on C18 column in eluent systems containing addition of acid or buffer at acidic pH. In these conditions, alkaloids are in ionic form, but dissociation of free silanol groups is suppressed. C8 stationary phase and mobile phase containing MeOH, water and trifluoroacetic acid (TFA) was used for separation of alkaloid brachycerine from callus cultures
Figure 4. HPTLC chromatogram by AMD of opium extract and standard alkaloids of opium: (1) morphine; (2) codeine; (3) thebaine; (4) papaverine; (5) noscapine; (6) opium extract; eluent used was universal gradient: methanol 100, methanol–dichloromethane 50/50, dichloromethane 100, dichloromethane 100, hexane100; derivatization by Dragendorff reagent [129].
Figure 5. Schematic diagram of bilateral band compression. A, initial period of the process; B, final stage of the compression. 1, foam to transfer the mobile phase for band compression; 2, mobile phase fronts. Arrows represent eluent movement for band compression; the arrow with curly brackets at the end indicates the effect on minor component [130].
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Table 2. Methods used for HPLC of alkaloids with mobile phase at acidic pH.
Pyrrolizidine alkaloids Boraginaceae species C18 MeCN/water H3PO4 UV [77]
Pyrrolizidine alkaloids Pittocaulon species C18 MeCN/water/TFA UV [236]
Pyrrolizidine alkaloids Echium glomeratum C18 MeCN/water/HCOOH MS [237]
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of Psychotria brachyceras [180]. Similar eluent system containing TFA was used for analysis of psychollatine, a major indole alkaloid glucoside from Psychotria umbellata [181]. Mobile phase containing 0.1% of formic acid was applied for analyses of terpenoid indole alkaloids from Catharanthus roseus hairy root cultures [182]. Ammonium formate buffer at pH 3.0 was added to mobile phase containing MeCN and water for analysis of mitragynine, an indole alkaloid occurring in Mitragyna
speciosa [183]. Volk developed a HPLC-RP method for separation of manifold biologically active indole alkaloids by using a mobile phase consisting of MeOH and acetate buffer at pH 3.2 [184]. Schliemann et al. separated indole alkaloids on C18 column in eluent containing MeCN/water and acetic acid or phosphoric acid [185]. Chromatographic analyses of the monoterpene indole alkaloid psychollatine were performed using a gradient based on MeOH/water/acetic acid [186]. Gonzalez-Vera
Senkirkine,senecionine Tussilago farfara C18 MeCN/water/HCOOH MS [74]
Pyrrolizidine alkaloids
Longitarsus jacobaeae, Oreina
cacaliae,and
O. speciosissima
C18 MeCN/water/TFA MS [239]
Quinolizidine alkaloids
Caulophyllum robustum C18 MeOH/MeCN/water/H3PO4 DAD [240]
Quinolizidine alkaloids Rat plasma C18 MeCN/water/HCOOH MS [241]
Diterpene alkaloids Rat plasma C18 MeCN/water/HCOOH DAD/TOFMS [242]
Diterpene alkaloids Human blood plasma C18 MeCN/water/HCOONH4/HCOOH MS [243]
Aconitine, hypaconitine, mesaconitine
Aconitum carmichaeli C18 MeCN/water/TFA UV [244]
Diterpene alkaloids Human plasma C18 MeOH/water/HCOOH MS/MS [245]
ContinuedTable 2. Methods used for HPLC of alkaloids with mobile phase at acidic pH.
Alkaloids Source Stationary phase
Eluent Detection Ref.
Figure 6. Schematic diagram of the interface components and the two positions of the six-port valve TLC/ESI-MS [132].
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et al. have satisfactory analysed indole alkaloids using eluents consisting of MeCN/water/TFA [187]. Ajmalicine and tetrahydroalstonine in Catharanthus cells were measured by HPLC in eluent system containing the addition of TFA [188]. Fernandez et al. have determined indole alkaloids from plant species of Papua New Guinea and Australia using MeOH/water/TFA as mobile phase on C18 column [189]. HPLC analysis of indoloquinoline alkaloids was performed by using eluent containing MeOH/water/ formic acid [190].
C18 column with eluent containing MeCN/water/HCOOH have been utilized for separation of hyoscyamnine and scopolamine from Datura inoxia plant extract [191]. Analysis of withanolides,tropane alkaloids, was achieved on C18 column with uses of MeOH/water/CH3COOH as mobile phase [192]. The mobile phase at pH 3.0 was applied for investigation of tropane alkaloids from Atropa beatica [193]. The quantification of hyoscyamine and scopolamine was performed on C18 column with MeCN/phosphate buffer at pH3.0
Table 3. Methods used for HPLC of alkaloids with mobile phase at basic pH.
Alkaloids Source Stationary phase
Eluent Detection Ref.
Nicotine, cotinine Human serum C8 MeCN/water/ammonia MS [254]Nicotine, cotinine, 3-hydroxycotinine meconium C18 MeCN/water/CH3COONH4/
NH4OH MS/MS [255]
Diterpene alkaloids Aconitum carmichaeli C18 MeCN/water/ammonia MS [70]
Body fluids C18 MeCN/water/ammonium bicarbonate/ammonia (pH 10.5) DAD [258]
Figure 7. HPLC–UV standard chromatogram of the selected alkaloids in acetonitrile (1.0 lg mL-1) at 205 nm (1: cytisine, 2: anabasine, 3: nicotine, 4: cotinine, 5: codeine (IS), 6: scopolamine, 7: brucine, 8: atropine, 9: colchicine, 10: strychnine, 11: harmine, 12: yohimbine, 13: ibogaine, 14: aconitine). Chromatographic separation was achieved on an EC NUCLEODUR Sphinx RP-C18 HPLC column using a mobile phase mixture of ACN and 0.01 M phosphate buffer pH 6.5 [179].
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[194]. Tropane alkaloids from Schizanthus grahamii were successfully analyzed on graphitic carbon column with eluent consisting MeCN/water/HCOOH [195]. The same acidic eluent system was applied for separation of antimuscarinic tropane alkaloids in plasma [196]. Bieri et al. separated alkaloids from the same plant by using carbon capillary column and acidic aqueous mobile phase containing acetic, formic or trifluoroacetic acids [197]. Basic eluents on the column containing ammonium formate were used also. For quantitative analysis of hyoscyamines, C18 stationary phase and mixture containing MeOH/water/HCOOH was applied [198]. Buffers for acidification of mobile phase acidic pH were rarely applied. Tropane alkaloids in animal plasma were analyzed on C18 column with eluent containing phosphate buffer at pH 3.1 [199].
The acidic eluents with addition of acetic acid [126] or TFA [200, 201] were used for analysis of colchicine. TFA was added to mobile phase containing MeCN/water for analysis of another phenethylamine alkaloid mescaline
[202]. The deactivated and encapped C18 column was applied for analysis of colchicine with eluent containing MeOH/water/HCOOH [59]. Eluent system with addition of acetic acid has also been used for separation and quantification of ergot alkaloids [203]. For the analysis of ergot alkaloids, Lolium perenne and Neotyphodium lolii, eluent containing MeCN/water/HCOOH was used [204]. Dong et al. were examined mobile phases at different acidic pH (3.6 - 5.6) for analysis of ephedra alkaloids [205].
Principal opium alkaloids were determined on C18 stationary phase with MeOH/water CH3COOH [206]. Phosphoric acid was added to acidification of mobile phase for analysis of opium alkaloids [207].
Many authors have described procedures for quantification of degradation of nicotine in tobacco by microorganisms. Zhong et al. conducted the analyze in chromatographic system: C18 – stationary phase, MeOH/water/KH2PO4 (pH 3) [208].
Figure 8. Total ion chromatograms of methanolic extract of Aconitum carmichaeli (a) and 15 authentic standards (b) by RRLC/TOFMS with a fragmentor voltage of 120V in positive ion mode. Chromatographic separation was carried out on an Agilent Zorbax Extend C18 column. The mobile phase consisted of 10mM ammonium acetate buffer solution adjusted to pH at 9.6±0.2 with 28% ammonia solution and ACN [253].
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Beyer et al. determined toxic alkaloids belonging to different chemical classes in human blood plasma on RP column with eluent containing MeCN and formate buffer at pH 3.5 [209].
Xanthine alkaloids were often analyzed in acidic eluent containing addition of phosphoric acid to aqueous-organic mobile phase [75,210].
Eluent systems at acidic pH were often applied for analysis of pyrrolizidine alkaloids in different samples (see Table 2). Most eluent systems for analysis of quinolizidine alkaloids by RP-LC contained the addition of different acids such as formic and phosphoric (Table 2).
5.2.2. Eluents at basic pHSilanol interaction can be reduced by using a high pH mobile phase, when free silanols are in ionized form but ionization of alkaloids is suppressed. The use of mobile phases at more basic pH, allowing effective suppression of analyte dissociation, is possible only by using specially prepared, high pH resistant stationary phases.
Lopez et al. have successfully separated vindolin and catharanthine on C18 stationary phase with mobile phase containing acetonitrile and acetic acid-ammonia buffer at pH 10 [178]. Indole alkaloids from Catharanthus roseus were analyzed on C18 column with mobile phase containing MeCN/water with addition of ammonia [179].The pharmacologically important terpenoid indole alkaloids from Catharanthus roseus hairy roots were analysed on C18 column in eluent system containing
mixture of MeCN and MeOH with addition of (NH4)2HPO4 (pH 7.3) [180]. Verma et al. applied a mixture of MeCN, MeOH and ammonium acetate buffer as mobile phase for separation of indole alkaloids from Catharanthus roseus [181]. Quantification of ajmalicine from shoot cultures of Catharanthus roseus was performed on C18 stationary phase and in eluent containing methanol and diammonium hydrogen phosphate [182]. Lactam ergot alkaloids in sclerotia of Claviceps purpurea were analysed on C8 stationary phase using a mixture of MeCN/water/(NH4)2CO3 as mobile phase [183]. The good separation of these alkaloids was obtained in a short time of analysis. A similar eluent system was applied for analysis of ergot alkaloids on C8 stationary phase [184]. Good separation of aconite alkaloids from the roots of Aconitum carmichaeli was obtained by LC coupled with time-of-flight mass spectrometry (TOFMS) in positive mode (Fig. 8) [185]. The mobile phase consisted of MeCN, water and acetate buffer at pH 9.6.
Other applications of chromatographic systems containing eluent at basic pH are presented in Table 3.
5.2.3. Eluents with addition of ion-pairing reagentsIon-pair chromatography (IPC) is often used in analysis of ionic samples. These are several hypotheses of ion-pairing in IP-RP systems and the mechanism is still discussed [259-263]. The first model assumes formation of ion-pair in polar liquid phase and adsorption of non-charged pair on the adsorbent surface [264-266]. The second model supposes ion-exchange mechanism with
Table 4. Methods used for HPLC of alkaloids with mobile phase containing ion-pairing reagents.
Palmatine and its metabolites Rat urine C18 MeOH/water/TEA MS/MS [304]
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adsorption of counter-ion on the hydrophobic adsorbent surface and formation of ion-exchange layer [267-270]. The next model is connected with dynamic process of formation of ion-exchanger with double electric layer on the adsorbent surface and dynamic equilibrium of analytes’ ions competing for the access to the layer [271].
Good results, symmetric peaks and good separation selectivity were obtained in eluent systems containing addition of ion pairing reagents. Gerasimenko et al. have separated indole alkaloids from Rauvolfia serpentina
and Rhazya stricta on C18 column using eluent containing MeCN, sodium dihydrogen phosphate and hexanesulphonic acid as ion pairing reagent [272]. The effect of the ion-pairing reagent or buffer concentrations and the pH of the mobile phase on the retention were examined (Fig. 9).
Due to ionic character of tropane alkaloids and their tendency for strong interactions with free silanol groups on surface silica matrix of the RP type stationary phases, ion-pair reagents are frequently used. Cardillo et al.
Figure 9. HPLC separation of the extracts of Rauvolfia serpentina x Rhazya stricta hybrid cell cultures (R x R17M) at day 5 after treatment with methyl jasmonate. The solvent system employed was: acetonitrile, sodium dihydrogen phosphate (3.9 mM) and hexanesulphonic acid (1.25 mM) at pH 2.5; (b) acetonitrile: sodium dihydrogen phosphate (3.9 mM) and hexanesulphonic acid (1.25 mM) at pH 5.5; and (c) acetonitrile:sodium dihydrogen phosphate (39 mM) and hexanesulphonic acid (2.5 mM) at pH 2.5 [272].
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performed HPLC analysis and quantification of tropane alkaloids from Brugmansia candida on RP column with MeOH/water containing octanesulfonic acid as ion pair reagent [273]. Octanesulfonic acid sodium salt was also used in addition to mobile phase for separation of hyoscyamine and scopolamine [274].
Kotzagiorgis et al. have determined pergolide, a semi-synthetic ergot alkaloid, by IPC in eluent system containing MeCN/water/sodium octanesulphonate [275]. They have used the method for determination of photo degradation products of the alkaloid. Ephedra alkaloids from Ephedra sinica and Citrus aurantium were analyzed with eluent system containing addition of SDS to aqueous mobile phase [276]. Eng et al. have also used an eluent system with addition of SDS for determination of ephedrine in medicinal plants [277].
IPC was also used for separation of opium alkaloids [278]. Opium samples were analyzed on C18 column with mobile phase containing MeCN, water, H3PO4 and heptane-1-sulfonic acid as ion-pairing reagent.
Quinine and 3-hydroxyquinine were determined in human plasma by IPC in eluent system: MeOH, MeCN, water, potassium dihydrogen phosphate and perchloric acid [279]. The method is simple, rapid, selective, reproducible and cost-effective. The method is also suitable for pharmacokinetic studies of quinine and 3-hydroquinine.
Cotinine, the main metabolite of nicotine in the human body, is widely used as a biomarker for assessment of direct or passive exposure to tobacco smoke. Yang et al. have determined the alkaloid in urine samples by IPC on C18 column with eluent containing MeCN/acetate buffer (pH 3.1)/sodium heptanesulfonate [280].
A simple and highly selective method, based upon solid-phase extraction (SPE), IPC and UV absorbance detection, was developed and validated by Liu et al. to determine alkaloids: lamivudine, oxymatrine and its active metabolite matrine in dog plasma [80]. They have performed analysis of alkaloids on C18 column with mixture of MeCN/water/H3PO4/sodium heptanesulfonate as eluent system.
5.2.4. Eluents with addition of silanol blockersSystems containing amines in eluents, which play the role of silanol blockers, are more effective. Thus the improvement of peak symmetry and the efficiency is noticed with narrow and very symmetric peaks. The more basic compound can strongly interact with residual silanols allowing the less basic compound to interact solely with the alkyl ligand of the stationary phase. The addition of basic silanol blocking agents causes two effects depending on the concentration of the blocking molecules: at lower concentrations they
are responsible for blocking of free silanols, leading to a decrease in the analyzed alkaloids’ retention, and, at higher concentrations, they cause an increase in alkaloid retention because of the suppression of the basic compounds’ retention.
Triethylamine was added to eluent containing MeOH, MeCN and aqueous ammonium acetate for separation of indole alkaloids from Catharanthus roseus [281]. Eluent system containing addition of triethylamine was used for separation of alkaloids from Hordeum species [282]. Triethylamine was added to mobile phase for separation of alkaloids from Catharanthus roseus [283,284]. Yang et al. described separation of vindoline, catharanthine and vinblastine from Catharanthus roseus [285]. Separation was performed in an eluent system containing a mixture of MeOH/MeCN/DEA/H3PO4 (pH7.5). HPLC system consisted of C18 stationary phase and a mixture of MeOH/MeCN/CH3COONH4/TEA has been employed for the analysis of monoterpenoid indole alkaloids from Catharanthus roseus [286].
Tropane alkaloids from Erythroxylum vacciniifolium were determined on C18 column in eluent system containing addition of TEA [287]. DEA was added to eluent for analysis of tropane alkaloids from hairy roots of Anisodus acutangulus [288].
Hong et al. were separated of ephedra alkaloids from Ephedra herb on polar-RP column with mixture of MeOH/water/phosphoric acid/TEA or MeOH/water/phosphoric acid/dibuthylamine [289].
To suppress free silanol groups, an addition of ionic liquids (IL) to mobile phases can also be applied. Their usefulness for analytical chemistry can be due to their favorable physicochemical properties, such as the lack of vapor pressure, good chemical and thermal stability, as well as very good dissolution properties regarding both inorganic and organic compounds. The retention mechanism using IL additives is very complex, since both the anion and the cation contribute to the retention of analytes. On the one hand, cations of ionic liquids coat the surface of the stationary phase to suppress free silanols and thus improve peak shape. On the other hand, part of the ionic liquids move with mobile phase and interact with the analytes – the anions of ionic liquids paired with the cations of analytes to make the analytes more retentive, whereas the cations of ionic liquids repulse the positively charged alkaloids to reduce their retention [290].
An ionic liquid-based aqueous two-phase system has been developed as a new pretreatment strategy for the analysis of opium alkaloids in Papaver papaveris plant extract [291]. The authors examined the effect of IL concentration on an alkaloid’s retention.
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In another study, Bian et al. performed a separation of marine-type alkaloids on C18 column with mobile phases containing addition of different ILs [292]. The authors examined the mechanism of separation of alkaloids in eluent systems with ILs additives. Influence of mobile phase pH, concentration of buffer, the effect of concentration of ILs and the length of ILs alkyl groups were also investigated. They have ascertained that the cations mostly interacted with the stationary phase silanol groups, and the anions were responsible for
the possible ion-pairing with the cationic solutes. The two effects were beneficial on the chromatographic separation.
The eluent systems containing the addition of silanol blockers such as TEA or DEA were often applied for analysis of diterpene alkaloids and alkaloids from different groups (see Table 4).
5.2.5. Selecting of stationary phasesGood results were obtained by selecting a stationary phase. Optimization of the stationary phase for analysis of alkaloids is mainly achieved by minimizing the interaction between analyte and residual silanols. The specific surface area of stationary phases depends on the chemical structure of the adsorbent and on the technology used in its manufacturing. Because of the solubility of alkaloids in aqueous and aqueous-organic modifier solvents, separation of alkaloids have been accomplished mainly on reversed-phase bonded silica gel. Silica supports are still superior to other supports in terms of efficiency, performance and rigidity. However, protonated alkaloids can interact with residual silanol groups on the stationary phases by ion-exchange mechanism. Thus, in addition to the typically reversed-phase retention mechanism, the ion-exchange mechanism also occurs, which often results in asymmetry of peaks, irreproducible retention, low performance of chromatographic systems and worse separation selectivity. Recently, polar-endcapped and polar-embedded RP phases with incorporated carbamate, amide or urea groups have moved to the center of interest. Besides the commonly used n-alkyl-type reversed-phase columns based on the immobilization of n-alkyl-type ligands onto a silica support, alternative hybrid RP-type phases providing additional interaction sites and properties due to embedded functional groups have become widely accepted and have gained increased importance. Alternatively, the introduction of hydrophobic π - π active aromatic moieties to the common n-alkyl chain RP-sites generates a concerted π - π reversed-phase retention mechanism, which, as a consequence of the new functionality, diversifies the common RP-interaction properties.
For example, atropine and scopolamine were successfully determined on pentafluorophenyl (PFP) stationary phase with MeCN/water/CH3COONH4 as mobile phase [305]. The influence of concentration of CH3COONH4 on retention and separation selectivity was investigated. The PFP column with the same mobile phase allowed an excellent separation of ephedrine alkaloids [306]. The authors optimized concentration of CH3COONH4 and column temperature for the best analyte separation in a short time. The peaks’ symmetry
Figure 10. Chromatograms of HPLC separations of quinines and quinidines on different stationary phases: a RP, b cSCX, c PSE-A. Didehydroquinidine (1), Didehydroquinine (2), Quinidine (3), Quinine (4), Dihydroquinidine (5), Dihydroquinine(6). Eluents: 5% ACN in water, 0.1% FA (RP), 37.5 mM NH4OAc in MeOH (cSCX), 12.5 mM NH4OAc in MeOH (PSE-A). UV detection at 254 nm [312].
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and theoretical plate number obtained for investigated alkaloids were also examined. The proposed method was applied for the phytochemical analysis of a variety of Ephedra samples including plant material. Santana et al. carried out a satisfactory separation and quantitative determination of ephedra akaloids – positional isomers p-synephrine and m-synephrine in bitter orange-containing supplements - on PFP stationary phase with a mobile phase containing MeOH/water/CH3COONH4 [307].
Determination of colchicine was performed on phenyl stationary phase with MeOH/water/ammonium acetate [308]. Phenyl column was useful for separation of opium alkaloids [309]. The eluent system contained MeOH, water and addition of ammonium acetate.
The phenyl-hexyl column was used for analysis of ergot alkaloids from Claviceps purpurea with a mixture of MeCN, water and ammonium carbamate as eluent [1]. The peaks obtained in the chromatographic system were symmetrical and well separated.
Separation of siniquici alkaloids in human serum after oral intake of a Heimia salicifolia extract were performed on phenylpropyl stationary phase using eluent containing MeCN/water/HCOOH [310].
Purine alkaloids from Camellia species were separated on amide-C16 column [311]. HPLC separation was performed by gradient elution. Mobile phase was composed of MeCN, water and H3PO4.
Different stationary phases – C18, chiral SCX and racemic strong cation exchanger PolySulfoethyl-A (PSE-A) - and different chromatographic modes –RP were applied for separation of quinine alkaloids (Fig. 10) [312].
Rarely, for separation of alkaloids, diol stationary phase was used. Heavner et al. have determined nicotine and their major metabolites in urine on diol column using 100% MeOH as eluent [313].
Zhu et al. determined caffeine and theophylline on ionic liquids-based monolithic column with mobile phase consisting aqueous solution of NaH2PO4 [314]. The authors comprised results obtained on non-ILs based monolithic column and ILs-based monolithic column and they obtained improvement of separation selectivity for ILs-based column.
5.2.6. TemperatureTemperature is another factor, which can be taken into account for the optimization of chromatographic separation. Temperature changes also caused changes in retention, system efficiency and peak symmetry. For ionizable compounds such as alkaloids, a change of temperature, not only changes the retention that can be observed, but also changes the pKa values of
compounds. Zhang et al. investigated the influence of temperature on retention of caffeine [315]. They have described the determination of caffeine on different RP columns at high temperature.
5.3. Chiral separationsThe HPLC enantiomeric separation of racemic indole alkaloids - tacamonine and related compounds was performed using Chiralpak AD and Chiralcel OD as chiral stationary phases and 2-propanol/hexane as mobile phase [316]. Chiralpak AD column was used for separation of enantiomers of meloscine [317].
Different tropane alkaloid enantiomers also vary pharmacokinetically, so that actual blood levels will result from dosing, different turnover and excretion kinetics. For this reason, separation and quantification of tropane alkaloid isomers are necessary. Simultaneous analysis of R- and S- hyoscamine was performed on chiral AGP column with eluent system containing MeCN/water/HCOONH4 [198].
For separation of ephedrine enantiomers, a chiral stationary phase of molecularly imprinted polymer (MIP) and mixture of MeCN/water/CH3COOH was successfully applied [2]. The recognition and binding of template molecules were based on interactions between amino and hydroxyl groups of the template and the carboxyl group of methacrylic acid, a host molecule in the MIP.
Separation of polycyclic indole alkaloids was performed by Lock and Waldmann on chiral stationary phase using mixture of tetrahydrofuran (THF) and n-hexane [318].
5.4. UPLC Recently UPLC technique was used for separation of alkaloids. UPLC allows better resolution, largely due to the small particle size and, with flow rates that approach common HPLC (0.1–1 mL min-1), UPLC offers fast separations. These advantages are important for sensitivity improvement and sample separation.
An ultra-performance liquid chromatography/ion mobility quadruple time-of-flight mass spectrometry (UPLC/IM-QTOF-MS) method was developed for profiling the indole alkaloids in yohimbe bark [319]. Mobile phase consisted of MeCN, water and aqueous ammonia.
UPLC was applied for analysis of scopolamine with eluent consisting of MeCN/formate buffer at pH 3.0 [320]. Rapid analysis of ergot alkaloids was carried by UPLC with MeOH/water/ammonia [321]. Sachin et al. determined piperine analogue using UPLC-gTOF-MS/MS method [71]. The analysis was performed on C18 column with MeOH/water as mobile phase. The method was used for a pharmacokinetic study.
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Zhou et al. proposed a rapid UPLC-MS/MS method for the determination of toxic pyrrolizidine alkaloids in plant extracts from Parasenecio and Senecio species [322]. UPLC analysis was performed on C18 stationary phase. The mobile phase was composed of MeCN and ammonia solution in water.
UPLC also has been applied for chromatographic analysis of isoquinoline alkaloids from Chelidonium majus [323]. Stationary phase in the method was C18 column and mobile phase containing MeCN and aqueous solution of ammonium acetate adjusted to pH 3.0 with acetic acid. Norisoboldine, one of the main bioactive isoquinoline alkaloids in Linderae radix, was determined by UPLC in chromatographic system C18 column- MeCN/water/HCOOH [324].
UPLC-MS/MS has been used for analysis of aconitine in plasma samples on C18 column where the acidic mobile phase was MeCN, water and HCOOH [325]. In another study, aconitine was determined by UPLC-MS/MS in basic eluent system consisting of MeCN and aqueous solution of ammonia (pH 11.0 – 11.2) [326].
Ibrahim et al. applied a capillary liquid chromatography (µHPLC) to separation of quinoline alkaloids using a mixture of MeOH, MeCN, water and CH3COONH4 as eluent [327]. µHPLC was also used for determination of quinine and chloroquinine in human serum This work reports the separation of two alkaloids on µHPLC with laser-induced fluorescence detector, the shortest time of analysis within 3 min and the lowest LOD (<2 fmol). A UPLC method for the identification and quantification of pharmaceutical preparations, containing paracetamol and/or acetyl salicylic acid, combined with anti-histaminics (phenylephrine, pheniramine maleate, diphenhydramine, promethazine) and/or alkaloids, quinine sulphate, caffeine or codeine phosphate, was developed (Fig. 11) [328]. The identification and quantification of these compounds was performed on C18 column by use an eleunt containing MeOH, water and ammonium acetate (pH4.0).
Separation of nicotine and related alkaloids was carried out on HILIC column [329]. Mobile phase consisted of MeCN, water, formate buffer at pH 3.0. The authors obtained good chromatographic results especially as coupled with short run times allowed by UHPLC and very good chromatographic performance, peak shape and enhanced sensitivity associated with HILIC mode.
5.5. MLCSome alkaloids were analyzed by use of micellar liquid chromatography (MLC). MLC differs from RP mode by the mobile phase, which contains a surfactant such as sodium dodecyl sulfate (SDS), cethyltrimethylammonium
bromide (CTAB) at a concentration higher than the critical micellar concentration, so that a part of the surfactant is present in the form of molecular aggregates – micelles. The retention of compounds is caused by the distribution of the molecules of analytes between aqueous mobile phase, the hydrophobic stationary phase and the micellar pseudo phase [266]. The use of addition of organic modifier causes increase of peak symmetry and system efficiency, reduces retention times, and changes the separation selectivity. Nicotine was determined in pharmaceuticals and biological fluids by the method on C18 column with a mobile phase containing SDS, penthanol and aqueous solution of NaH2PO4 and KCl with electrochemical detection. MLC method was also used for analysis of piperine in different plant extracts [267]. The analysis was conducted on C18 stationary phase in eluent system containing propanol, water, NaH2PO4 and SDS.
5.6. HILICHydrophilic interaction chromatography (HILIC) is a liquid chromatography technique that uses polar stationary phases – silica or a polar bonded phases in conjunction with a mobile phase containing an appreciable quantity of water combined with a higher proportion of a less polar solvent (often acetonitrile). HILIC is important for the separation of highly polar substances. Good results have been obtained especially for alkaloids with small molecules, which are weakly retained in RP-LC mode.The benzodioxole-indole alkaloids from Narcissus were determined by HPLC-MS on HILIC column with the linear gradient of mobile phase containing MeOH/MeCN/aqueous 1 mM ammonium acetate [332]. Vuppala et al. have described analysis of mitragynine in rat plasma on UPLC HILIC column with a mobile phase consisting of MeCN/HCOONH4/HCOOH [333]. The method showed excellent sensitivity, linearity, precision, accuracy and was successfully applied to evaluate the pharmacokinetic parameters after intravenous administration of mitragynine to rats.
For separation of cocaine and their metabolites, Giroud et al. achieved HILIC mode separation with MeCN/CH3COONH4 at pH 4.5 as eluent [334].
Iwasaki et al. presented a sensitive and specific method HILIC-MS/MS method for the simultaneous quantification and detection of nicotine and its metabolites in human maternal and cord sera [68]. The separation was achieved on HILIC column with mobile phase containing MeCN, water and HCOOH.
5.7. ICEDifferent retention mechanism in ion-exchange chromatography (ICE) often leads to quite different
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Figure 11. Chromatograms of HPLC separations of pharmaceutical preparations. HPLC was performed on an Acquity UPLC TM system. The gradient was performed on Acquity BEH C18 column, starts at 95% ammonium acetate buffer pH 4 and 5% methanol. The initial conditions are kept for 1 min, before going to a plateau of 50% buffer and 50% methanol in 9 min [328].
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separation selectivity of ionic compounds. High efficiencies and symmetrical peaks can be obtained by IEC using relatively simple eluents (buffer or organic/buffer mixtures). Retention of compounds in this method depends primarily on the kind of stationary phases, the ionic strength of eluent (kind and concentration of buffer), pH and in some cases the addition of organic modifiers. Nakamura et al. performed determination of atropine and scopolamine on strong cation exchange (SCX) column with mixture containing MeCN/water/KH2PO4/H3PO4 as mobile phase [335]. A mixture of MeCN/water HNO3 was used as eluent for separation of ephedra alkaloids by ion chromatography [336]. The authors studied the effect of concentration of MeCN or HNO3 on retention of analyzed alkaloids. The method has been applied successfully to the determination of these compounds in Ephedra herbs and in pharmaceutical preparations.
Good separation and symmetrical peaks were obtained for alkaloids belonging to phenylethylamine derivatives by IEC method. HPLC separation and quantification of psychoactive herbal phenylethylamine alkaloids in human plasma was performed on SCX column with mobile phase containing MeCN/water/HCOONH4/HCOOH at pH 3.0 [107].
Morgan et al. analyzed quinine and quinidine on SCX column using eluent containing MeOH, water and ammonium perchlorate [337]. The high efficiencies, good peak shapes and fast analysis times were obtained.
Cation exchange column was applied for analysis of pilocarpine [338]. Mixture of MeOH and aqueous solution of HCOONH4 was used in the method as the mobile phase.
5.8. Preparative HPLCPreparative HPLC method was used for purification of indole alkaloidal fractions of plant extracts [339]. The isolation of indole alkaloids on semiprepartive scale was performed by HPLC. Eluents used in preparative HPLC for isolation or purification of different indole alkaloids often consisted of a mixture of organic modifier (usually MeOH) and water without addition of buffers or other reagents. Ma et al. have isolated alkaloids from Uncaria rhynchophylla plant extract on C18 preparative column using mixture of methanol and water as eluent [340]. Purification of Mitragyna inermis plant extract fraction containing oxindole alkaloids was performed on silica column with dichloromethane and acetone as mobile phase [161]. Gradient elution on preparative C18 column was used for purification of alkaloidal fraction from Cortinarius brunneus [341]. The alkaloidal fraction obtained from Malassezia furfur was purified on C8
preparative column in gradient eluent system containing MeCN and water [342,343]. Two monoterpene indole alkaloids were separated on preparative C18 column using MeOH and water eluent system [344]. Sarker et al. have separated methanolic extract from Centaurea cyanus on C18 preparative HPLC column using as eluent mixture of MeOH and water [345]. Cytotoxic bisindole alkaloids from Melodinus fusiformis were isolated by preparative RP-HPLC with aqueous methanolic eluent [346]. Semi-preparative C18 DB column was applied for final purification of alkaloidal fractions obtained from Penicillium crustosum [347]. Mixture of MeOH and water was used for purification of extract fractions obtained from Neonauclea sessilifolia [348], Uncaria villosa [349], Bupleurum chienese [350], Aspergillus fumigatus [351], Isatis indigotica [352], and Candida albicans [353]. The eluent containing MeOH/THF/water was applied for purification of alkaloidal fractions from Alstonia angustiloba [354]. Mixture of MeCN and water composed mobile phase was used for preparative separation of (bis)indole alkaloids isolated from Aplysinopsis reticulata [355]. The preparative HPLC method has also been used for purification of alkaloidal fraction obtained from Gelsemium elegans [356]. The eluent in this method consisted of a mixture of MeOH and water with addition of DEA. The purification of plant extract obtained from Alstonia pneumatophora was carried out in eluent at acidic pH (MeOH/water/TFA) [357]. A similar eluent system containing MeCN/water/TFA has also been used for purification of alkaloidal fractions obtained from Alstonia macrophylla [188].
Preparative HPLC C18 column with eluent of MeOH/water/H3PO4 was applied for purification of alkaloid fractions obtained from Merremia genus plant extracts [358]. Separation of alkaloids from Datura metel was performed on preparative C18 column with a mixture of MeOH and water as mobile phase [359]. Ephedra alkaloids from a traditional Chinese medicinal herb – Ephedra sinica – were isolated in a chromatographic system: silica gel column as a stationary phase and MeOH/CHCl3 as an eluent [360].
Tetrahydrobenzylisoquinoline alkaloids were isolated by preparative HPLC in RP system [361]. Casale et al. have performed preparative isolation of opium alkaloids on C18 column with eluent consisting of MeCN/water/TFA [362].
Nyshiyama et al. used preparative HPLC for separation of tertiary isoquinoline alkaloids from Xylopia parviflora [363]. Separation was performed on C18 column with mobile phase containing MeCN, water and HClO4.
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6. ConclusionsAlkaloids from different chemical groups have been widely analyzed by different LC methods. Several separation and detection methods have been developed and applied for the qualitative and quantitative analysis in plant materials, extracts, dietary supplements, body fluids and other natural samples.
Most TLC separation often coupled with densitometry is carried out on silica gel plates with nonaqueous eluents consisting of mixtures of MeOH, CHCl3, AcOEt, CH2Cl2, and Me2CO. Addition of ammonia or amines such as DEA or TEA to mobile phase was often applied for improvement of spot shape and separation selectivity. Good separation of alkaloids and system efficiency was obtained by use of special development TLC technique such as 2D TLC or AMD.
In most cases, HPLC analysis of alkaloids is performed in RP systems. Some alkaloids (tropane, xanthine) were successfully determined in eluent systems containing only organic modifier and water or buffer at neutral pH, but most alkaloids in such eluent systems are poorly separated and peaks obtained on chromatograms are very asymmetrical. Therefore, eluents at acidic pH, obtained by addition of acids or appropriate buffers, were often applied in analysis of alkaloids from all groups. If
pH silanol ionization is suppressed, then it could lead to a decrease of retention, improvement of peak shape and system efficiency. Rarely, for separation of alkaloids mobile phases at basic pH were used when ionization of investigated compounds is suppressed. Good symmetry of peaks and good separation selectivity has been obtained in eluent systems containing addition of ion pairing reagents. Very good results were received in many cases when silanol blockers, such as amines, were added to eluents. Good results were also obtained by selecting a stationary phase. Optimization of the stationary phase for analysis of basic compounds, such as alkaloids, is achieved by minimizing the interaction between analyte and residual silanols.
Use of UPLC methods for analysis of some alkaloids allows for better resolution and significant decrease of analysis time.
Alternative HPLC methods such as HILIC and ICE have gained increasing attention and have been applied to the selective and rapid analysis of selected alkaloids. The high efficiencies, good peak shapes and fast analysis times were obtained by using these methods.
LC-hyphenated techniques such as LC-MS and LC-NMR are especially attractive providing both chromatographic and, at least, partial structural information simultaneously.
C. Müller, H.S. Klaffke, W. Krauthause, R. Wittkowski, Mycotoxin Research 22, 197 (2006)K. Balamurugan, K. Gokulakrishnan, T. Prakasam, Arabian Journal of Chemistry (2011) (In press) doi:10.1016/j.arabjc.2011.06.024D. Sykora, E. Tesarova, M. M. Popl, J. Chromatogr. A 758, 37 (1997).T. Fornstedt, G. Zhong, G. Guichon, J. Chromatogr.A. 741, 1 (1996)J. Wang, Y. Zheng, T. Efferth, R. Wang, Y. Shen, X.Hao, Phytochemistry 66, 697 (2005)B. Hemmateenejad, A. Abbaspour, H. Maghami, R. Miri, M.R. Panjehshahin, Anal. Chem. Acta 575, 209 (2006)J. Penelle, P. Christen, J. Molgo, M. Tits, V. Brandt, M. Frederich, L. Angenot, Phytochemistry 58, 619 (2001)K. Keplinger, G. Laus, M. Wurm, M.P. Dierich, H. Teppner, J. Ethnopharmacol. 64, 23 (1999Y.D. Rattmann, M.R. Terluk, W.M. Souza, C.A.M. Santos, M.W. Biavatti, L.B. Torres, S. Mesia-Vela, L. Rieck, J.E. da Silva-Santos, M.C.A. de Marques, J. Ethnopharmacol. 100, 268 (2005)
G. Laus, D. Brossner, K. Keplinger, Phytochemistry 45, 855 (1997)J. Wang, C. Machado, D.G. Panaccione, H.-F.Tsai, C.L. Schardl, Fungal Genet.Biol. 41, 189 (2004)F. Berthiller, M. Sulyok, R. Krska, R. Schuhmacher, Int. J. Food Microbiol. 119, 33 (2007) H. Takayama, Y. Matsuda, K. Masubuchi, A. Ishida, M. Kitaima, N. Aimi, Tetrahedron 60, 893 (2004)R. Pilarski, H. Zielińsk, D. Ciesiołka, K. Gulewicz, J. Ethnoparmacol. 104, 18 (2006)J. Zhang, Y. Yu, D. Liu, Z. Liu, Phytomedicine 14, 50 (2007)V. Fragoso, N.C. do Nascimento, D.J. Moura, A.C.R. Silva, M.F. Richter, J. Saffi, A.G. Fett-Neto, Toxicology in Vitro 22, 559 (2008)S. Uhling, D. Petersen, Toxicon 52, 175 (2008)J.C.A. Tanaka, C.C. da Silva, I.C.P. Ferreira, G.M.C. Machado, L.L. Leon, A.J.B. de Oliveira, Phytomedicine 14, 377 (2007)I. Brondz, D. Ekeberg, K. Høiland, D. S. Bell, A.R. Annino, J. Chromatogr. A 1148, 1 (2007)W.-F. Fong, C. Wang, G.-Y. Zhu, C.-H. Leung, M.-S. Yang, H.-Y. Cheung, Phytomedicine 14, 160 (2007)
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827
Analysis of alkaloids from different chemical groups by different liquid chromatography methods
828Unauthenticated
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Analysis of alkaloids from different chemical groups by different liquid chromatography methods
830Unauthenticated
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829
Analysis of alkaloids from different chemical groups by different liquid chromatography methods
830Unauthenticated
Download Date | 1/24/20 7:14 PM
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831
Analysis of alkaloids from different chemical groups by different liquid chromatography methods
832Unauthenticated
Download Date | 1/24/20 7:14 PM
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831
Analysis of alkaloids from different chemical groups by different liquid chromatography methods
832Unauthenticated
Download Date | 1/24/20 7:14 PM
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Analysis of alkaloids from different chemical groups by different liquid chromatography methods
834Unauthenticated
Download Date | 1/24/20 7:14 PM
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834Unauthenticated
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A. Petruczynik
835
Analysis of alkaloids from different chemical groups by different liquid chromatography methods
