Recent Advances in Asymmetric Catalysis Using p-Block Elements.

The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone of organic synthesis. Typically, metal catalysts bearing chiral ligands as well as chiral organocatalysts have been employed for the enantioselective synthesis of organic compounds. In this review, we highlight the recent advances in main group catalysis for enantioselective reactions using the p-block elements (boron, aluminium, phosphorus, bismuth) as a complementary and sustainable approach to generate chiral molecules. Several of these catalysts benefit in terms of high abundance, low toxicity, high selectivity, and excellent reactivity. This minireview summarises the utilisation of chiral p-block element catalysts for asymmetric reactions to generate value-added compounds.

Fertilization can modify the enantioselective persistence of penthiopyrad in relation to the co-influence on soil ecological health.

Penthiopyrad is a widely used chiral fungicide for controlling rust and Rhizoctonia diseases. Development of optically pure monomers is an important strategy to realize amount reduction and increment effects of penthiopyrad, wherein, fertilizers as the co-exiting nutrient supplement may alter the enantioselective residues of penthiopyrad in soil. In our study, influences of urea, phosphate, potash, NPK compound, organic granular, vermicompost and soya bean cake fertilizers on enantioselective persistence of penthiopyrad were fully evaluated. This study demonstrated that R-(-)-penthiopyrad dissipated faster than S-(+)-penthiopyrad during 120 days. High pH, available nitrogen, invertase activities and reduced available phosphorus, dehydrogenase, urease, catalase activities were situated to benefit removing the concentrations of penthiopyrad and weakening enantioselectivity in soil. With respect to the impact of different fertilizers on soil ecological indicators, vermicompost contributed to enhanced pH. Urea and compound fertilizer played an absolute advantage in promoting available nitrogen. All fertilizers didn't go against available phosphorus. Dehydrogenase responded negatively to phosphate, potash and organic fertilizers. Urea increased invertase, besides, it and compound fertilizer both diminished urease activity. The catalase activity was not activated by organic fertilizer. Based on all the findings, soil application of urea and phosphate fertilizers was recommended and considered as a better option to exhibit high efficiency for the dissipation of penthiopyrad. The combined environmental safety estimation can effectively guide the treatment of fertilization soils in line with the nutrition requirements and pollution regulation from penthiopyrad.

Enantioselective Synthesis of Atropisomeric Biaryl Phosphorus Compounds by Chiral-Phosphonium-Salt-Enabled Cascade Arene Formation.

Axially chiral biaryl monophosphorus molecules, exemplified by atropisomeric 1,1'-biaryl aminophosphines, are significant motifs in numerous chiral ligands/catalysts. Developing efficient methods for preparing phosphorus compounds with these privileged motifs is an important endeavor in synthetic chemistry. Herein, we develop an effective, modular method by a chiral-phosphonium-salt-catalyzed novel cascade between phosphorus-containing nitroolefins and α,α-dicyanoolefins, leading to a great diversity of atropisomeric biaryls bearing phosphorus groups in high yields with excellent stereoselectivities. The reaction features include a Thorpe-type cycloaddition/oxidative hydroxylation/aromatization cascade pathway with a central-to-axial chirality transfer process. Insight gained from our studies is expected to advance general efforts towards the catalytic synthesis of atropisomeric biaryl phosphorus compounds, offering a platform for developing new efficient chiral ligands and catalysts.

Separation and determination of cysteine enantiomers in plasma after derivatization with 4-fluoro-7-nitrobenzofurazan.

The importance of D-amino acids in mammals associated with enantio-dependent biological functions has been increasingly highlighted. In addition to naturally occurring, D-amino acid supplementation could have a positive biological impact, including cytoprotective implications. In this context, supplementation with D-cysteine has revealed beneficial effects. Quantification of cysteine enantiomers in rodent plasma has been achieved by using 4-fluoro-7-nitrobenzofurazan derivatization of the target analytes. Cystine, the main form of cysteine in the plasma, was initially reduced to cysteine using DL-dithiothreitol. Baseline enantioseparation was then achieved in less than 3 min using a (R,R)-Whelk-O 1 stationary phase and isocratic elution using CH3OH-H2O 90:10 (v/v) with 15 mM ammonium formate (apparent pH 6.0) at 0.5 mL/min. The derivatives were then detected using negative ESI-MS in SRM mode. An external calibration was employed for D-cysteine, while L-cysteine quantification, as an endogenous analyte, was addressed using a background subtraction strategy. The method was validated. Response functions were obtained from 0 to 300 µM and from 0 to 125 µM for D-cysteine and L-cysteine, respectively. The trueness ranged from 96% to 105% for both enantiomers with repeatability and intermediate precision lower than 8% and 15% for the D-form and the endogenous L-form, respectively. The method was successfully applied for determining D- and L-cysteine in mouse plasma after D-cysteine administration.

Gas chromatography of essential oil: State-of-the-art, recent advances, and perspectives.

This review is an overview of the recent advances of gas chromatography in essential oil analysis; in particular, it focuses on both the new stationary phases and the advanced analytical methods and instrumentations. A paragraph is dedicated to ionic liquids as gas chromatography stationary phases, showing that, thanks to their peculiar selectivity, they can offer a complementary contribution to conventional stationary phases for the analysis of complex essential oils and the separation of critical pairs of components. Strategies to speed-up the analysis time, thus answering to the ever increasing request for routine essential oils quality control, are also discussed. Last but not least, a paragraph is dedicated to recent developments in column miniaturization in particular that based on microelectromechanical-system technology in a perspective of developing micro-gas chromatographic systems to optimize the energy consumption as well as the instrumentation dimensions. A number of applications in the essential oil field is also included.

Determination of enantiomeric and stable isotope ratio fingerprints of active secondary metabolites in neroli (Citrus aurantium L.) essential oils for authentication by multidimensional gas chromatography and GC-C/P-IRMS.

Neroli essential oil (EO), extracted from bitter orange blossoms, is one of the most expensive natural products on the market due to its poor yield and its use in fragrance compositions, such as cologne. Multiple adulterations of neroli EO are found on the market, and several authentication strategies, such as enantioselective gas chromatography (GC) and isotope ratio mass spectrometry (IRMS), have been developed in the last few years. However, neroli EO adulteration is becoming increasingly sophisticated, and analytical improvements are needed to increase precision. Enantiomeric and compound-specific isotopic profiling of numerous metabolites using multidimensional GC and GC-C/P-IRMS was carried out. These analyses proved to be efficient for geographical tracing, especially to distinguish neroli EO of Egyptian origin. In addition, δ2H values and enantioselective ratios can identify an addition of 10% of petitgrain EO. These results demonstrate that enantioselective and stable isotopic metabolite fingerprint determination is currently a necessity to control EOs.

Assessment of the contribution of chiral odorants to aroma property of baked green teas using an efficient sequential stir bar sorptive extraction approach.

Chiral volatile compounds are known to be distributed in teas at various enantiomeric ratios. However, the performance of each enantiomer, including aroma characteristics, aroma intensities, and contribution to the overall flavor of tea, is still unclear. In this study, aroma characteristics and intensities of 38 volatile enantiomers in standards and baked green teas with chestnut-like aroma and clean aroma were evaluated by an efficient sequential headspace-stir bar sorptive extraction (seq-HS-SBSE) approach combined with the enantioselective gas chromatography-olfactometry/mass spectrometry (Es-GC-O/MS) technique. Moreover, aroma recombination results for the two types of baked green teas using 14 chiral odorants and four achiral odorants indicated that the combinations of the detected odorants mainly contributed to the "floral", "sweet", and "chestnut-like" aromas. R-Linalool simultaneously enhanced the "floral", "sweet", and "chestnut-like" aromas; R-limonene mainly contributed to the "sweet" and "clean" aromas; and S-α-terpineol promoted the "sweet" and "floral" aromas of baked green tea.

Asymmetric Synthesis of Tetrasubstituted α-Aminophosphonic Acid Derivatives.

Due to their structural similarity with natural α-amino acids, α-aminophosphonic acid derivatives are known biologically active molecules. In view of the relevance of tetrasubstituted carbons in nature and medicine and the strong dependence of the biological activity of chiral molecules into their absolute configuration, the synthesis of α-aminophosphonates bearing tetrasubstituted carbons in an asymmetric fashion has grown in interest in the past few decades. In the following lines, the existing literatures for the synthesis of optically active tetrasubstituted α-aminophosphonates are summarized, comprising diastereoselective and enantioselective approaches.

Chemistry of the chippiine/dippinine/tronocarpine class of indole alkaloids.

The chippiines/dippinines/tronocarpine are a family of biologically and structurally interesting polycyclic tryptamine-derived indole alkaloids isolated from the leaf and bark extracts of plants belonging to the Tabernaemontana genus. To date, 14 members of this family have been isolated and characterized. This review discusses the isolation, structure determination, biological activity, and proposed biosynthesis of these metabolites. In addition, synthetic studies on the alkaloids are described including approaches to tronocarpine and dippinine B core intermediates and total syntheses of (+)-dippinine B and (+)-tronocarpine.

Study of Volatile Secondary Metabolites Present in Piper carpunya Leaves and in the Traditional Ecuadorian Beverage Guaviduca.

Piper carpunya Ruiz & Pav. is an aromatic shrub native to Ecuador, the leaves of which are used to prepare the traditional beverage Guaviduca. Different health benefits are attributed to the guaviduca beverage, which is consumed as a traditional and folk medicine. In this study, fresh P. carpunya leaves were collected in the winter and summer and subjected to hydrodistillation for the extraction of the essential oil. The guaviduca beverage was prepared by infusion in water and the volatile compounds were isolated by liquid-liquid extraction. Chemical composition and enantioselective analyses were performed by gas chromatography. The antibacterial activity was assayed against Gram-positive and Gram-negative bacteria. The scavenging radical properties of the essential oil was evaluated by 2,2-diphenyl-1-picrylhydryl (DPPH) and 2,2'-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) assays. The acetylcholinesterase inhibitory activity was measured using the spectrophotometric method. The chemical analysis allowed us to identify more than 98% of the compounds in all samples. The main constituent of the essential oil was 1,8-cineole (25.20 ± 1.31%) in P. carpunya collected in winter and (17.45 ± 2.33%) in P. carpunya collected in summer, while in the beverage, there was 14 mg/L. Safrole was identified in the essential oil (PCW 21.91 ± 2.79%; PCS 13.18 ± 1.72%) as well as in the beverage (2.43 ± 0.12 mg/L). Enantioselective analysis was used to investigate the enantiomeric ratio and excess of four chiral components. The essential oil presented a strong activity against Klebsiella pneumoniae with a MIC of 500 µg/mL and a very strong anticholinesterase activity with an IC50 of 36.42 ± 1.15 µg/mL.

Immobilization of 6-O-α-maltosyl-ß-cyclodextrin on the surface of black phosphorus nanosheets for selective chiral recognition of tyrosine enantiomers.

A novel chiral sensing platform, 6-O-α-maltosyl-ß-cyclodextrin (Mal-ßCD)-based film, is proposed for selective electrochemical recognition of tyrosine (Tyr) enantiomers. Black phosphorus nanosheets (BP NSs) and Mal-ßCD modified glassy carbon electrode (Mal-ßCD/BP NSs/GCE) were prepared by a layer-to-layer drop-casting method, and the platform was easy to fabricate and facile to operate. It is proposed that the amino and hydroxyl groups of the Tyr enantiomers and the chiral hydroxyl groups of Mal-ßCD selectively form intermolecular hydrogen bonds to dominate effective chiral recognition. Two linear equations of Ip (µA) = 11.40 CL-Tyr (mM) + 0.28 (R2 = 0.99147) and Ip (µA) = 7.96 CD-Tyr (mM) + 0.22 (R2 = 0.99583) in the concentration range 0.01-1.00 mM have been obtained. The limits of detection (S/N=3) for L-Tyr and D-Tyr were 4.81 and 6.89 µM, respectively. An interesting phenomenon was that the value of IL-Tyr/ID-Tyr (1.51) in this work was slightly higher than the value of IL-Trp/ID-Trp (1.49) reported in our previous study, where tryptophan (Trp) enantiomers were electrochemically recognized by Nafion (NF)-stabilized BPNSs-G2-ß-CD composite. The two similar sensors fabricated by different methods showed different recognition ability toward either Tyr or Trp enantiomers, and the underlying mechanism was discussed in detail. More importantly, the proposed chiral sensor enables prediction of the percentages of D-Tyr in racemic Tyr mixtures. The chiral sensor may provide a novel approach for the fabrication of novel chiral platforms in the practical detection of L- or D-enantiomer in racemic Tyr mixtures.Graphical abstract.

Enantioselective residue analysis of oxathiapiprolin and its metabolite in tea and other crops by ultra-high performance liquid chromatography-tandem mass spectrometry.

Oxathiapiprolin is the first chiral piperidinyl thiazole isoxazoline fungicide developed to control downy mildew and other diseases, and there were no prior reports on its enantiomeric residue. In this study, a modified quick, easy, cheap, effective, rugged, and safe extraction and purification method followed by ultra-high performance liquid chromatography-tandem mass spectrometry determination was first developed and validated for the residue analysis of oxathiapiprolin enantiomers and its metabolite IN-E8S72 in green tea and other crops. Oxathiapiprolin enantiomers and IN-E8S72 were separated on a chiral Lux Cellulose-3 column with the use of 0.1% formic acid in acetonitrile and 5 mmol/L ammonium acetate in water as mobile phases. IN-E8S72 was eluted first, followed by (-)-oxathiapiprolin, and then (+)-oxathiapiprolin. The recoveries ranged from 53.3 to 125.3% with relative standard deviations ranging from 1.4 to 16.0%. The limits of quantification for (-)-oxathiapiprolin and (+)-oxathiapiprolin were 0.005 mg/kg in romaine lettuce, head cabbage, potato, grape, and garlic, 0.01 mg/kg in soybean and pea, and 0.025 mg/kg in green tea and dry pepper. The limits of quantification of IN-E8S72 were twice those of (-)-oxathiapiprolin. Screening results with real market samples indicated that there was no enantiomeric excess in the oxathiapiprolin residue in romaine lettuce.

A novel, enantioselective, thermostable recombinant hydantoinase to aid the synthesis of industrially valuable non-proteinogenic amino acids.

Overexpression of a novel hydantoinase (hyuH) from P. aeruginosa (MCM B-887) in E. coli yielded optically pure carbamoyl amino acids. The use of optically pure carbamoyl amino acids as substrates facilitates the synthesis of non-proteinogenic amino acids. The enzyme hyuH shared a maximum of 92 % homology with proven hydantoinase protein sequences from the GenBank database, highlighting its novelty. Expression of hydantoinase gene was improved by >150 % by overexpressing it as a fusion protein in specialized E. coli CODON + host cells, providing adequate machinery for effective translation of the GC-rich gene. The presence of distinct residues in the substrate binding and active site of MCM B-887 hydantoinase enzyme explained its unique and broad substrate profile desirable for industrial applications. The purified enzyme, with a specific activity of 53U/mg of protein, was optimally active at 42 °C and pH 9.0 with a requirement of 2 mM Mn2+ ions. Supplementation of 500 mM of Na-glutamate enhanced the thermostability of the enzyme by more than 200 %.

A magnetic multi-walled carbon nanotube preparative method for analyzing asymmetric carbon, phosphorus and sulfur atoms of chiral pesticide residues in Chinese herbals by chiral liquid chromatography-quadrupole/linear ion trap mass spectrometry determination.

An analytical method for the determination of asymmetric carbon, phosphorus and sulfur atoms in chiral pesticide residues by magnetic multi-walled carbon nanotube sample pretreatment combined with chiral ultra-performance liquid chromatography/quadrupole/linear ion trap mass spectrometry (UPLC-MS/Qtrap) was developed and applied to chiral pesticide residues analysis in Chinese herbals. Eleven different chiral pesticides were found, and 36.4% were positive in Chinese herbals. Three plants containing detectable pesticide residues were observed in Dendrobium nobile, Panax notoginseng flowers and honeysuckle, in the order of decreasing detected concentration. High detection frequencies of 26.1% for (R/S)-(±)-difenoconazole and 14.5% for (R/S)-(±)-metalaxyl and (R/S)-(±)-propiconazole were observed, the residual amount for (R/S)-(±)-difenoconazole, (R/S)-(±)-metalaxyl and (R/S)-(±)-propiconazole were 0.32 ~ 2.5 mg/kg, 0.022 ~ 0.23 mg/kg, 0.62 ~ 3.21 mg/kg respectively. The EF value of (R/S)-(±)-difenoconazole was 0.506 ± 0.046. The EF value of (R/S)-(±)-metalaxyl was lower than 0.5 in Dendrobium nobile, Panax notoginseng flowers, Panax notoginseng roots and hawthorn. The EF of (R/S)-(±)-propiconazole was not significantly enantioselective in honeysuckle and Panax notoginseng flowers. The enantioselectivity of various pesticide residues in different plants cannot be predicted from our existing knowledge and may closely depend on plant growth, environmental conditions or molecular structure.

Simultaneous Enantioselective Determination of Two New Isopropanol-Triazole Fungicides in Plant-Origin Foods Using Multiwalled Carbon Nanotubes in Reversed-Dispersive Solid-Phase Extraction and Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry.

A simple and sensitive enantiomeric analytical method was established for the determination of two new isopropanol-triazole fungicides mefentrifluconazole and ipfentrifluconazole in plant-origin foods using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The best enantioseparation of the four target stereoisomers was achieved on a Chiral MX(2)-RH column within 7 min by reversed-phase liquid chromatography, which is a significant improvement in the resolution of different chiral compounds under one set of conditions. A simple and effective pretreatment procedure was developed for the extraction and purification of the two target chiral fungicides using reversed-dispersive solid-phase extraction (r-DSPE) with multiwalled carbon nanotubes (MWCNTs). The influence of the type and amount of MWCNTs on the purification efficiencies and recoveries was evaluated. The mean recoveries for all four stereoisomers were in the range of 76.9-91.2%, with relative standard deviation (RSD) values below 7.2%. The limit of quantification (LOQ) of all stereoisomers of mefentrifluconazole and ipfentrifluconazole was 5 µg/kg for all tested matrixes. The results of the method validation and real samples analysis confirm that the established method is efficient and reliable for the enantiomeric determination of mefentrifluconazole and ipfentrifluconazole in plant-origin food samples.

Optimized one-pot derivatization and enantioseparation of cysteine: Application to the study of a dietary supplement.

Cysteine is a sulfur-containing amino acid which plays an outstanding role in many biological pathways in mammals. The analysis and quantification of native cysteine remains a critical issue due to its highly reactive thiol group evolving to the disulfide cystine derivative through oxidation reaction. Aimed at improving the derivative stability, cysteine was labelled with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), which reacts with both amino and thiol groups. The derivatization was optimized and the chemical identity of the reaction product was assessed via high-resolution mass spectrometry. The NBD-cysteine derivative resulted stable for 10 days. This derivative was enantioresolved (α and RS equal to 1.25 and 2.70, respectively) thanks to a (R,R)-Whelk-O1 phase with the following chromatographic setting: eluent, MeOH/water-90/10 (v/v) with 15 mM ammonium formate (pwsH 6.0); column temperature, 35 °C; flow rate, 1.0 mL/min. The developed method was validated following the ICH guidelines and applied for the quality control of a L-cysteine containing dietary supplement.

The biological activities of prothioconazole enantiomers and their toxicity assessment on aquatic organisms.

Chiral fungicide prothioconazole has a wide range of antifungal spectrum; however, little research has been conducted to evaluate prothioconazole on an enantiomeric level. Five target pathogens and three common aquatic organisms were tested for the enantioselective bioactivity and toxicity of prothioconazole in this work. The antifungal activity of the enantiomers against wheat phytoalexin, rice blast fungus, exserohilum turcicum, Alternaria triticina, and Fusarium avenaceum was determined, and it was found that (-)-prothioconazole were 85 to 2768 times more active than (+)-prothioconazole toward these target organisms. In order to reflect the risk to aquatic ecosystem, the acute toxicity of the enantiomers to Daphnia magna, Chlorella pyrenoidosa, and Lemna minor L. was assessed. It was observed that the toxicity of (-)-prothioconazole to D. magna was 2.2 times higher than (+)-prothioconazole, but it was lower to C. pyrenoidosa and L. minor L. The toxicities of (+)-enantiomer and (-)-enantiomer to D. magna and C. pyrenoidosa were synergy, indicating that the racemate had higher threat to the organisms. It could be concluded that the effects of prothioconazole on target organisms and the acute toxicity to nontarget species were enantioselective with (-)-enantiomer possessing higher efficiency and lower toxicity. Such enantiomeric differences should be taken into consideration when assessing the performance of prothioconazole.

Investigation of free and conjugated seleno-amino acids in wheat bran by hydrophilic interaction liquid chromatography with tandem mass spectrometry.

An analytical method for determining seleno-methionine, methyl-seleno-cysteine, and seleno-cystine in wheat bran was developed and validated. Four different extraction procedures were evaluated to simultaneously extract endogenous free and conjugated seleno-amino acids in wheat bran in order to select the best extraction protocol in terms of seleno amino acid quantitation. The extracted samples were subjected to a clean-up by a reversed phase/strong cation exchange solid-phase extraction and analyzed by chiral hydrophilic interaction liquid chromatography-tandem mass spectrometry. The optimized extraction protocol was employed to validate the methodology. Process efficiency ranged from 58 to 112% and trueness from 73 to 98%. Limit of detection and limit of quantification were lower than 1 ng/g. Four wheat bran samples were analyzed for both total Se and single seleno-amino acids determination. The results showed that Se- seleno-methyl-lselenocysteine was the major seleno-amino acid in wheat bran while seleno-methionine and seleno-cysteine were both minor species.

Application and enantioselective residue determination of chiral pesticide penconazole in grape, tea, aquatic vegetables and soil by ultra performance liquid chromatography-tandem mass spectrometry.

Penconazole is a typical triazole fungicide with wide use on fruits, vegetables, and tea plants to control powdery mildew. In the present study, an efficient graphite carbon black solid phase extraction (GCB-SPE) purification combined with chiral ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method was developed for determination of penconazole enantiomers in different complex matrices, including grape, tea, soil, lotus root, lotus leaf, lotus seed and hulls. The method was then applied to investigate the enantioselective dissipation of penconazole enantiomers in a real field experiment of grape and soil. As a result, a satisfactory separation of penconazole enantiomers on a chiral Lux Cellulose-2 column (150 mm × 2 mm i.d., 3 µm) was obtained with 0.1% formic acid in methanol and 10 mmol L-1 ammonium acetate in water (75/25, v/v) as mobile phase at 0.25 mL min-1. The enantiomer (+)-penconazole was firstly eluted, and (-)-penconazole was then eluted. The method showed reliable performances in linearity, recovery and precision, the recoveries of (+)-penconazole and (-)-penconazole in all of six matrices were between 70.5% and 121.0% with the relative standard deviations (RSDs) ranging from 0.8% to 23.6% at the low, medium and high spiked levels. The limits of quantitation (LOQs) of this method were lower than 0.0025 mg kg-1 in grape, soil and lotus root, 0.005 mg kg-1 in lotus leaf, lotus seed meat and lotus seed shell, and 0.0125 mg kg-1 in tea. Results of field trials indicated that (-)-penconazole degraded faster than its (+)-isomer in grape. While only a moderate stereoselectivity was observed in soil, with (-)-penconazole preferential degraded. The proposed method could be used to investigate enantioselective environmental behavior of penconazole enantiomers in complex matrices. And results in this study could provide useful information on realistic risk assessment of penconazole in grape.

Direct chromatographic study of the enantioselective biodegradation of ibuprofen and ketoprofen by an activated sludge.

The quantification of the enantiomeric fraction (EF) during the biodegradation process is essential for environmental risk assessment. In this paper the enantioselective biodegradation of ibuprofen, IBU, and ketoprofen, KET, two of the drugs most consumed, was evaluated. Biodegradation experiments were performed in batch mode using a minimal salts medium inoculated with an activated sludge (collected from a Valencian Waste Water Treatment Plant) and supplemented with the racemate of each compound. The inoculum activity was verified using fluoxetine as reference compound. The experimental conditions used (analyte concentration and volume of inoculum) were chosen according to OECD guidelines. In parallel, the optical density at 600 nm was measured to control the biomass growth and to connect it with enantioselectivity. Two RPLC methods for chiral separations of IBU and KET using polysaccharides-based stationary phases were developed. Novel calculations and adapted models, using directly the chromatographic peak areas as dependent variable, were proposed to estimate significant parameters related to the biodegradation process: biodegradation (BD) and EF values at given time, half-life times of (R)- and (S)-enantiomers, number of days to reach a complete BD and the minimum EF expected. The modelled BD and EF curves fitted adequately the data (R2 > 0.94). The use of these new equations provided similar results to those obtained using concentration data. However, the use of chromatographic peak areas data, eliminates the uncertainty associated to the use of the calibration curves. The results obtained in this paper indicate that an enantiorecognition towards IBU enantiomers by the microorganisms present in the activated sludge used in this study occurred, being the biodegradation of (R)-IBU higher than that of (S)-IBU. For KET, non-enantioselective biodegradation was observed.