N.R. Neng

Adsorptive micro-extraction techniques—Novel analytical tools for trace levels of polar solutes in aqueous media

A novel enrichment technique, adsorptive μ-extraction (AμE), is proposed for trace analysis of polar solutes in aqueous media. The preparation, stability tests and development of the analytical devices using two geometrical configurations, i.e. bar adsorptive μ-extraction (BAμE) and multi-spheres adsorptive μ-extraction (MSAμE) is fully discussed. From the several sorbent materials tested, activated carbons and polystyrene divinylbenzene phases demonstrated the best stability, robustness and to be the most suitable for analytical purposes. The application of both BAμE and MSAμE devices proved remarkable performance for the determination of trace levels of polar solutes and metabolites (e.g. pesticides, disinfection by-products, drugs of abuse and pharmaceuticals) in water matrices and biological fluids. By comparing AμE techniques with stir bar sorptive extraction based on polydimethylsiloxane phase, great effectiveness is attained overcoming the limitations of the latter enrichment approach regarding the more polar solutes. Furthermore, convenient sensitivity and selectivity is reached through AμE techniques, since the great advantage of this new analytical technology is the possibility to choose the most suitable sorbent to each particular type of application. The enrichment techniques proposed are cost-effective, easy to prepare and work-up, demonstrating robustness and to be a remarkable analytical tool for trace analysis of priority solutes in areas of recognized importance such as environment, forensic and other related life sciences.

Powdered activated carbons as effective phases for bar adsorptive micro-extraction (BAμE) to monitor levels of triazinic herbicides in environmental water matrices

Bar adsorptive micro-extraction using three powdered activated carbons (ACs) as adsorbent phases followed by liquid desorption and high performance liquid chromatography with diode array detection (BAμE(ACs)-LD/HPLC-DAD), was developed to monitor triazinic herbicides (atrazine, simazine and terbutylazine) in environmental water matrices. ACs used present apparent surface areas around 1000 m(2) g(-1) with an important mesoporous volume and distinct surface chemistry characteristics (pH(PZC) ranging from 6.5 to 10.4). The textural and surface chemistry properties of the ACs adsorbent phases were correlated with the analytical data for a better understanding of the overall enrichment process. Assays performed on 10 mL water samples spiked at the 10.0 μg L(-1) levels under optimized experimental conditions yielded recoveries around 100% for the three herbicides under study. The analytical performance showed good precision (RSD<15.0%), convenient detection limits (≈0.1 μg L(-1)) and suitable linearity (1.0-12.0 μg L(-1)) with good correlation coefficients (r(2)>0.9914). By using the standard addition method, the application of the present method on real water matrices, such as surface water and wastewater, allowed very good performances at the trace level. The proposed methodology proved to be a suitable sorptive extraction alternative for the analysis of priority pollutants with polar characteristics, showing to be easy to implement, reliable, sensitive and requiring a low sample volume to monitor triazinic compounds in water matrices.

Antioxidant and antibacterial activity of essential oil and extracts of bay laurel Laurus nobilis Linnaeus (Lauraceae) from Portugal

Laurus nobilis L. is an aromatic plant frequently used as a spice in Mediterranean cookery and as a traditional medicine for the treatment of several infectious diseases. The aim of this study was to characterise the antibacterial and antioxidant activities of bay laurel essential oil (EO), ethanolic extract (EE) and hot/cold aqueous extract (AE). The major components detected in bay laurel EO were eucalyptol (27.2%), α-terpinenyl acetate (10.2%), linalool (8.4%), methyleugenol (5.4%), sabinene (4.0%) and carvacrol (3.2%). The EO exhibited strong antibacterial activity against all tested foodborne spoilage and pathogenic bacteria, whereas this activity was less pronounced or even nonexistent in the EE and AE. In contrast, EO exhibited low antioxidant activity compared to extracts (EX), and among the EX, the hot AE revealed the highest antioxidant ability. The results show that bay laurel EO and its EX have potential as natural alternatives to synthetic food preservatives, in order to enhance food safety and increase food shelf life.

Antioxidant and cytotoxic activities of carob tree fruit pulps are strongly influenced by gender and cultivar.

Extracts from fruit pulps of six female cultivars and two hermaphrodite Portuguese carob trees [(Ceratonia siliqua L., Fabaceae)] exhibited strong antioxidant activity and were rich in phenolic compounds. The extracts decreased the viability of different human cancer cell lines on a dose- and time-dependent manner. Gender and cultivar significantly influenced the chemical content and the biological activities of the extracts. Extracts from hermaphrodite trees had a higher content of phenolic compounds, and exhibited higher antioxidant and cytotoxic activities. Among females, cv. Aida had the highest radical scavenging activity and total content of phenolics, Mulata the highest capacity to inhibit lipid oxidation and Gasparinha the strongest cytotoxic activity on HeLa cells. The decrease in cell viability was associated with apoptosis on HeLa and MDA-MB-231 lines. (+)-Catechin and gallic acid (GA) were the main compounds identified in the extracts, and GA contributed to the antioxidant activity. Our results show that the antioxidant and cytotoxic activities of carob tree fruit pulps are strongly influenced by gender and cultivar, and provide new knowledge about the advantages of hermaphrodite trees over female cultivars, namely, as a source of compounds with biological interest, which may represent an increase of their agronomic interest.

Cork-based activated carbons as supported adsorbent materials for trace level analysis of ibuprofen and clofibric acid in environmental and biological matrices

In this contribution, powdered activated carbons (ACs) from cork waste were supported for bar adsorptive micro-extraction (BAμE), as novel adsorbent phases for the analysis of polar compounds. By combining this approach with liquid desorption followed by high performance liquid chromatography with diode array detection (BAμE(AC)-LD/HPLC-DAD), good analytical performance was achieved using clofibric acid (CLOF) and ibuprofen (IBU) model compounds in environmental and biological matrices. Assays performed on 30 mL water samples spiked at the 25.0 μg L(-1) level yielded recoveries around 80% for CLOF and 95% for IBU, under optimized experimental conditions. The ACs textural and surface chemistry properties were correlated with the results obtained. The analytical performance showed good precision (<15%), suitable detection limits (0.24 and 0.78 μg L(-1) for CLOF and IBU, respectively) and good linear dynamic ranges (r(2)>0.9922) from 1.0 to 600.0 μg L(-1). By using the standard addition methodology, the application of the present approach to environmental water and urine matrices allowed remarkable performance at the trace level. The proposed methodology proved to be a viable alternative for acidic pharmaceuticals analysis, showing to be easy to implement, reliable, sensitive and requiring low sample volume to monitor these priority compounds in environmental and biological matrices.

Determination of tributyltin in environmental water matrices using stir bar sorptive extraction with in-situ derivatisation and large volume injection-gas chromatography–mass spectrometry

Stir bar sorptive extraction with in-situ derivatization using sodium tetrahydridoborate (NaBH4) followed by liquid desorption and large volume injection-gas chromatography-mass spectrometry detection under the selected ion monitoring mode (SBSE(NaBH4)in-situ-LD/LVI-GC-MS(SIM)) was successfully developed for the determination of tributyltin (TBT) in environmental water matrices. NaBH4 proved to be an effective and easy in-situ speciation agent for TBT in aqueous media, allowing the formation of adducts with enough stability and suitable polarity for SBSE analysis. Assays performed on water samples spiked at the 10.0μg/L, yielded convenient recoveries (68.2±3.0%), showed good accuracy, suitable precision (RSD<9.0%), low detection limits (23ng/L) and excellent linear dynamic range (r(2)=0.9999) from 0.1 to 170.0µg/L, under optimized experimental conditions. By using the standard addition method, the application of the present methodology to real surface water samples allowed very good performance at the trace level. The proposed methodology proved to be a feasible alternative for routine quality control analysis, easy to implement, reliable and sensitive to monitor TBT in environmental water matrices.

Development of a Powdered Activated Carbon in Bar Adsorptive Micro-Extraction for the Analysis of Morphine and Codeine in Human Urine

In the present work, bar adsorptive microextraction using an activated carbon (AC) adsorbent phase followed by liquid desorption and high-performance liquid chromatography with diode array detection was developed to monitor morphine (MOR) and codeine (COD) in human urine. Under optimized experimental conditions, assays performed in aqueous media spiked at the 30.0 µg/L level yielded recoveries of 41.3 ± 1.3% for MOR and 38.4 ± 1.7% for COD, respectively. The textural and surface chemistry properties of the AC phase were also correlated with the analytical data for a better understanding of the overall enrichment process. The analytical performance showed good precision (relative standard deviation < 8.0%), suitable detection limits (0.90 and 0.06 µg/L for MOR and COD, respectively) and convenient linear dynamic ranges (r(2) > 0.991) from 10.0 to 330.0 µg/L. By using the standard addition methodology, the applications of this analytical approach to water and urine matrices allowed remarkable performance to monitor MOR and COD at the trace level. This new confirmatory method proved to be a suitable alternative to other sorptive micro-extraction methodologies in monitoring trace levels of opiate-related compounds, because it was easy to implement, reliable, sensitive and required a low sample volume.

Application of bar adsorptive microextraction (BAμE) for anti-doping control screening of anabolic steroids in urine matrices.

This study proposes a new analytical methodology for the determination of trace levels of testosterone (T) and epitestosterone (E) in urine matrices using bar adsorptive microextraction combined with liquid desorption followed by high-performance liquid chromatography with diode array detection (BAμE-LD/HPLC-DAD). The comparison of different sorbent coatings (five activated carbons, one styrene-divinylbenzene, two modified pyrrolidone, one ciano and one n-vinylpyrrolidone polymers) through BAμE showed that the latter phase presented much higher selectivity and capacity offering multiple mechanisms of interaction. Assays using this phase were performed on 25mL of water samples spiked at the 8.0μg/L level, yielded average recoveries of 92.1 and 93.4% for T and E, respectively, under optimized experimental conditions; BAμE (n-vinylpyrrolidone): 16h (1000rpm), pH 5.5; LD: acetonitrile, 30min under sonication treatment. From the developed analytical methodology, suitable detection limits were achieved (0.4μg/L) and good linear dynamic ranges (1.4-16.0μg/L) with remarkable determination coefficients (r(2)>0.9978). By using the standard addition methodology, the application of the present analytical approach on urine samples revealed good sensitivity. The proposed method, which operated under the floating sampling technology, proved to be a suitable sorption-based static microextraction alternative for screening T, E and the T/E ratio in urine samples for doping control purposes. The methodology showed to be easy to implement, demonstrating good reproducibility, sensitivity and robustness, allowing the possibility to choose the most selective sorbent coating according to the compounds of interest.

Enhancement for trace analysis of sulfonamide antibiotics in water matrices using bar adsorptive microextraction (BAμE)

In this study, the enhancement for trace analysis of sulfonamide antibiotics (sulfathiazole, sulfamethoxazole and sulfadimethoxine) and trimethoprim in water matrices is proposed using bar adsorptive microextraction combined with micro-liquid desorption followed by high-performance liquid chromatography with diode array detection (BAμE-μLD/HPLC-DAD). By comparing different polymers and activated carbons as sorbent coatings for BAμE, the polystyrene-divinylbenzene polymer (PS-DVB) showed the best selectivity for the compounds under study. Assays performed through BAμE(PS-DVB)-μLD on 25mL of ultrapure water samples spiked at the 8.0μgL(-1) level showed recoveries ranging from 63.8±1.5% to 84.2±1.9%, under optimized experimental conditions. The validated method provided satisfactory limits of detection (0.08-0.16μgL(-1)) and good linear dynamic ranges (0.16-8.00μgL(-1)) with determination coefficients higher than 0.9958. The proposed analytical methodology was applied to real matrices, such as tap, estuarine and wastewater samples using the standard addition method. It showed to be easy to implement, with good reproducibility, sensitivity and requiring small amount of sample. Furthermore, negligible consumption of organic solvents was used in compliance with the green analytical chemistry principles. When compared to other well-established microextraction approaches, BAμE demonstrated better performance concerning recovery yields and sensitivity.

Bar adsorptive microextraction (BAμE) coated with mixed sorbent phases-Enhanced selectivity for the determination of non-steroidal anti-inflammatory drugs in real matrices in combination with capillary electrophoresis.

The present work proposes the application of bar adsorptive microextraction coated with mixed sorbent phases (n-vinylpyrrolidone and divinylbenzene polymers with strong and weak anion exchangers), combined with liquid desorption followed by capillary electrophoresis with diode array detection (BAμE(PMIX)-LD/CE-DAD) for the determination of trace levels of non-steroidal anti-inflammatory drugs (NSAIDs: salicylic acid, mefenamic acid, diclofenac and naproxen as model compounds) in urine and water matrices. Assays performed on 25mL of water samples spiked at the 80.0μg/L level, yielded average recoveries between 86.6 and 104.% for all the NSAIDs under study using optimized experimental conditions. The proposed analytical methodology demonstrated suitable detection limits (0.3μg/L) and good linear dynamic ranges (2.5-320.0μg/L) with determination coefficients higher than 0.9981. By using the standard addition methodology, the present analytical approach was applied on urine and water samples, where good selectivity and sensitivity were achieved. The proposed method, which operated under the floating sampling technology, proved to be a suitable sorption-based static microextraction alternative for monitoring trace levels of NSAIDs in urine and water samples. The methodology showed to be easy to implement, demonstrating good reproducibility and robustness, allowing the possibility to choose the most selective sorbent, or mixed sorbent phases, according to the compounds of interest.