Residuo de Elaeis guineensis (Arecaceae) como absorbente de combustibles para aplicación pasiva en ingeniería contra incendios / Elaeis guineensis (Arecaceae) residue as a fuel sorbent for passive application in fire-fighting engineering

Resumen Introducción: Los vertidos de líquidos inflamables pueden producir accidentes graves, principalmente en plantas industriales y en carretera. Para prevenir la dispersión de derrames, se utilizan diversas formas de recolecta, como la absorción con sólidos porosos. Residuos agroindustriales pueden ser aprovechados como materiales sorbentes de líquidos inflamables. Objetivo: Determinar la capacidad de absorción de las biomasas residuales del pedúnculo de la palma aceitera (Elaeis guineensis) y del endocarpio del fruto de coyol (Acrocomia sp.) para cuatro líquidos orgánicos inflamables. Métodos: Las biomasas residuales de E. guineensis y de Acrocomia sp. se evaluaron como sorbentes para combustibles derramados (diésel, queroseno de aviación, queroseno comercial y gasolina). Se midió la cantidad de líquido absorbida por las biomasas a 24 ºC durante una semana, y su cinética de desorción a 50 ºC, usando balanzas de secado. Resultados: La propiedad sorbente del material de Acrocomia sp. no fue satisfactoria, comparada con el pedúnculo de E. guineensis, debido a diferencias en arquitectura residual del material orgánico. Esta última biomasa muestra una capacidad de absorción para los combustibles de 2.4 ± 0.2 cm3 g-1 a 24 ºC. La diatomita absorbe mayor cantidad de los combustibles estudiados, pero la difusión de estos fluidos a 50 ºC por la matriz mineral es solo 0.26 ± 0.09 veces lo observado para el material de E. guineensis, como resultado del mayor grado de tortuosidad de los poros de la diatomita. Conclusiones: El pedúnculo de palma aceitera (E. guineensis) mostró un adecuado potencial desempeño para la aplicación pasiva en la mitigación de los riesgos de incendio, con respecto a la diatomita. El endocarpio del fruto de Acrocomia sp. no resultó útil para esta operación de recuperación.

Abstract Introduction: Spills of flammable liquids can lead to serious accidents, mainly in industrial plants and on roads. To prevent the spread of spills, various forms of collection are used, such as absorption with porous solids. Agroindustrial waste can be used as sorbent materials for flammable liquids. Objective: To determine the sorption capacity of the residual empty-fruit bunch of oil-palm (Elaeis guineensis) and the macaw palm (Acrocomia sp.) nutshell for four organic flammable liquids. Methods: The residual biomasses of E. guineensis and Acrocomia sp. were assessed as sorbents for spilled fuels (diesel, jet fuel, commercial kerosene, and gasoline). Volumetric measurement of liquid-fuel absorption at 24 ºC was taken during a week. Desorption was measured at 50 ºC as the drying kinetics, by using moisture scales. Results: The sorption capacity of the Acrocomia sp. material was not satisfactory, compared to the E. guineensis residual material, due to differences in the residual architecture of the organic material. This last can absorb 2.4 ± 0.2 cm3 g-1 at 24 ºC, during a one-week period. Diatomite absorbs greater quantities of the organic liquids but, the fluids diffusion at 50 ºC is 0.26 ± 0.09 times more slowly in the mineral matrix, because of the greater pore tortuosity in this mineral matrix. Conclusions: The oil-palm empty fruit bunch of E. guineensis, showed lesser but adequate performance than the sorbing behavior for fire hazard mitigation of diatomite. The nutshell of macaw palm (Acrocomia sp.) did not prove to be useful for this recovery operation.

Magnetic particle spray mass spectrometry for the determination of beta-blockers in plasma samples.

Magnetic particle spray mass spectrometry (MPS-MS), an innovative ambient ionization technique proposed by our research group, was employed to determine beta-blockers in human plasma samples. A dispersive solid phase extraction of atenolol, metoprolol, labetalol, propranolol, nadolol, and pindolol was carried out using magnetic molecularly imprinted polymer (M-MIP) particles that were attached to the tip of a metal probe, which was placed in the mass spectrometer inlet. A solvent (1% formic acid in methanol) was dispensed on the particles, and the Taylor cone was formed around them (in high voltage). The analytes were desorbed/ionized and determined by a triple quadrupole mass spectrometer. M-MIP was synthesized with oxprenolol as a pseudo-template, demonstrating good selectivity to beta-blockers compared with no-analog molecules, with an adsorption process occurring in monolayers, according to isotherm studies. Kinetic experiments indicated chemisorption as the predominant M-MIP/analyte interaction. The analytical curves were linear (R2 > 0.98), and the limit of quantification was 3 µg L-1 for all the analytes. Limits of detection ranged from 0.64 to 2.41 µg L-1. Precisions (relative standard deviation) and accuracies (relative error) ranged from 3.95 to 21.20% and -17.05 to 18.93%, respectively. MPS-MS proved to be a simple, sensitive, and advantageous technique compared with conventional approaches. The analyses were fast, requiring no chromatographic separation and without ionic suppression. The method is aligned with green chemistry principles, requiring minimal sample, solvent, and sorbent amounts. MPS-MS successfully integrates sample preparation and ambient ionization mass spectrometry and holds great potential for application with other sorbents, samples, and analytes.

Advances and Applications of Hybrid Graphene-Based Materials as Sorbents for Solid Phase Microextraction Techniques.

The advancement of traditional sample preparation techniques has brought about miniaturization systems designed to scale down conventional methods and advocate for environmentally friendly analytical approaches. Although often referred to as green analytical strategies, the effectiveness of these methods is intricately linked to the properties of the sorbent utilized. Moreover, to fully embrace implementing these methods, it is crucial to innovate and develop new sorbent or solid phases that enhance the adaptability of miniaturized techniques across various matrices and analytes. Graphene-based materials exhibit remarkable versatility and modification potential, making them ideal sorbents for miniaturized strategies due to their high surface area and functional groups. Their notable adsorption capability and alignment with green synthesis approaches, such as bio-based graphene materials, enable the use of less sorbent and the creation of biodegradable materials, enhancing their eco-friendly aspects towards green analytical practices. Therefore, this study provides an overview of different types of hybrid graphene-based materials as well as their applications in crucial miniaturized techniques, focusing on offline methodologies such as stir bar sorptive extraction (SBSE), microextraction by packed sorbent (MEPS), pipette-tip solid-phase extraction (PT-SPE), disposable pipette extraction (DPX), dispersive micro-solid-phase extraction (d-µ-SPE), and magnetic solid-phase extraction (MSPE).

Preparation of a sustainable magnetic sorbent for the extraction and preconcentration of progestogens in natural water samples.

A film composed of agarose and graphene (G) and magnetic nanoparticles (G-MNPs) is proposed as a sorbent for the extraction and determination of medroxyprogesterone (MED), levonorgestrel (LEV), norethisterone (NOR) and progesterone (PRO) in natural water samples. Both the preparation of the film and the extraction procedure were optimized. The optimal extraction parameters were as follows: isopropyl alcohol as activation solvent, sample pH value of 3.0, extraction time of 30 min, 1.00 mL of acetonitrile as eluent, elution time of 5 min and sample volume of 100.00 mL. HPLC with photodiode array detector was used for the separation and determination. The method presented a linear range between 2.50 and 75.0 µg L-1 for all analytes, and the LODs were between 1.40 and 1.80 µg L-1. The method was applied to natural water samples, obtaining satisfactory recovery values (75-111 %). In conclusion, for the immobilization of the G-MNPs, agarose was used, which is a non-toxic, renewable and biodegradable material. The G-MNPs-agarose film was reused up to 70 times, without losing its extraction capacity significantly and presenting excellent sorbent properties, which allow the extraction and preconcentration of the progestogens under study.

Green analytical toxicology method for determination of synthetic cathinones in oral fluid samples by microextraction by packed sorbent and liquid chromatography-tandem mass spectrometry.

PURPOSE: We developed and validated a method for quantitative analysis of ten synthetic cathinones in oral fluid (OF) samples, using microextraction by packed sorbent (MEPS) for sample preparation followed by liquid chromatography‒tandem mass spectrometry (LC‒MS/MS). METHOD: OF samples were collected with a Quantisal™ device and 200 µL was extracted using a C18 MEPS cartridge installed on a semi-automated pipette and then analyzed using LC‒M/SMS. RESULTS: Linearity was achieved between 0.1 and 25 ng/mL, with a limit of detection (LOD) of 0.05 ng/mL and a limit of quantification (LOQ) of 0.1 ng/mL. Imprecision (% relative standard deviation) and bias (%) were better than 11.6% and 7.5%, respectively. The method had good specificity and selectivity against 9 different blank OF samples (from different donors) and 68 pharmaceutical and drugs of abuse with concentrations varying between 400 and 10,000 ng/mL. No evidence of carryover was observed. The analytes were stable after three freeze/thaw cycles and when kept in the autosampler (10 °C) for up to 24 h. The method was successfully applied to quantify 41 authentic positive samples. Methylone (mean 0.6 ng/mL, median 0.2 ng/mL), N-ethylpentylone (mean 16.7 ng/mL, median 0.35 ng/mL), eutylone (mean 39.1 ng/mL, median 3.6 ng/mL), mephedrone (mean 0.5 ng/mL, median 0.5 ng/mL), and 4-chloroethcathinone (8.1 ng/mL) were quantified in these samples. CONCLUSION: MEPS was an efficient technique for Green Analytical Toxicology purposes, which required only 650 µL organic solvent and 200 µL sodium hydroxide, and the BIN cartridge had a lifespan of 100 sample extractions.

Automated microextraction by packed sorbent of endocrine disruptors in wastewater using a high-throughput robotic platform followed by liquid chromatography-tandem mass spectrometry.

An automated microextraction by packed sorbent followed by liquid chromatography-tandem mass spectrometry (MEPS-LC-MS/MS) method was developed for the determination of four endocrine disruptors-parabens, benzophenones, and synthetic phenolic antioxidants-in wastewater samples. The method utilizes a lab-made repackable MEPS device and a multi-syringe robotic platform that provides flexibility to test small quantities (2 mg) of multiple extraction phases and enables high-throughput capabilities for efficient method development. The overall performance of the MEPS procedure, including the investigation of influencing variables and the optimization of operational parameters for the robotic platform, was comprehensively studied through univariate and multivariate experiments. Under optimized conditions, the target analytes were effectively extracted from a small sample volume of 1.5 mL, with competitive detectability and analytical confidence. The limits of detection ranged from 0.15 to 0.30 ng L-1, and the intra-day and inter-day relative standard deviations were between 3 and 21%. The method's applicability was successfully demonstrated by determining methylparaben, propylparaben, butylated hydroxyanisole, and oxybenzone in wastewater samples collected from the São Carlos (SP, Brazil) river. Overall, the developed method proved to be a fast, sensitive, reliable, and environmentally friendly analytical tool for water quality monitoring.

Evaluation of Organofunctionalized Polydimethylsiloxane Films for the Extraction of Furanic Compounds.

Hybrid membranes with three different thicknesses, PMDS_C1, PMDS_C2, and PMDS_C3 (0.21 ± 0.03 mm, 0.31 ± 0.05 mm, and 0.48 ± 0.07 mm), were synthesized by the sol-gel method using polydimethylsiloxane, hydroxy-terminated, and cyanopropyltriethoxysilane. The presence of cyano, methyl, and silicon-methyl groups was confirmed by FTIR analysis. Contact angle analysis revealed the membranes' hydrophilic nature. Solvent resistance tests conducted under vortex and ultrasonic treatments (45 and 60 min) demonstrated a preference order of acetonitrile > methanol > water. Furthermore, the membranes exhibited stability over 48 h when exposed to different pH conditions (1, 3, 6, and 9), with negligible mass losses below 1%. The thermogravimetric analysis showed that the material was stable until 400 °C. Finally, the sorption analysis showed its capacity to detect furfural, 2-furylmethylketone, 5-methylfurfural, and 2-methyl 2-furoate. The thicker membrane was able to adsorb and slightly desorb a higher concentration of furanic compounds due to its high polarity provided by the addition of the cyano groups. The results indicated that the membranes may be suitable for sorbent materials in extracting and enriching organic compounds.

Direct magnetic sorbent sampling flame atomic absorption spectrometry (DMSS-FAAS) for highly sensitive determination of trace metals.

A procedure of direct magnetic sorbent sampling in flame atomic absorption spectrometry (DMSS-FAAS) was developed in this work. Metal-loaded magnetic sorbents were directly inserted in the flame of the FAAS for direct metal desorption/atomization. Magnetic graphene oxide aerogel (M-GOA) particles were synthesized, characterized, and used as a proof-of-concept in the magnetic dispersive solid phase extraction of Pb2+ ions from water samples. M-GOA was selected because is a light and porous sorbent, with high adsorption capacity, that is quickly burned by the flame. Magnetic particles were directly inserted in the flame by using a metallic magnetic probe, thereby avoiding the need for a chemical elution step. As all the extracted Pb2+ ions arrive to the flame without passing through the nebulization system, a drastic increase in the analytical signal was achieved. The improvement in the sensitivity of the proposed method (DMSS-FAAS) for Pb2+ determination was at least 40 times higher than the conventional procedure in which the Pb2+ is extracted, eluted, and analyzed by conventional flame atomic absorption spectrometry (FAAS) via the nebulization system. The analytical curve was linear from 5.0 to 180.0 µg L-1 and the limit of detection was found to be 1.30 µg L-1. Background measurements were insignificant, and the atomic absorption peaks were narrow and reproducible. Precision assessed as a percentage of the relative standard deviation %RSD was found to be 17.4, 7.1, and 7.8% for 10, 70, and 180 µg L-1 levels, respectively. The method showed satisfactory results even in the presence of other ions (Al3+, Cr3+, Co2+, Cu2+, Fe3+, Mn2+, Ba2+, Mg2+, and Li+). The performance of the new system was also evaluated for Cd2+ ions, as well as by using other magnetic particles available in our lab: magnetic carbon nanotubes (M-CNTs), magnetic restricted access carbon nanotubes (M-RACNT), magnetic poly (methacrylic acid-co-ethylene glycol dimethacrylate) (M-PMA), magnetic nanoparticles coated with orange powder peel (M-OPP), and magnetic nanoparticles covered with SiO2 (M - SiO2). Analytical signals increased for both analytes in all sorbents (increases of about 4-37 times), attesting the high potential and applicability of the proposed method. Simplicity, high analytical frequency, high detectability and reproducibility, low cost, and possibility of being totally mechanized are the most relevant advantages.

Lead determination in commercial juice samples by direct magnetic sorbent sampling flame atomic absorption spectrometry (DMSS-FAAS).

The direct magnetic sorbent sampling flame atomic absorption spectrometry (DMSS-FAAS), recently proposed by our research group, was applied to determine the lead in soy-based juice, whole grape juice, reconstituted grape juice, and orange nectar samples. A dispersive solid phase extraction (d-SPE) of lead was carried out using a magnetic orange peel powder, developed and optimized by Gupta et al (2012), that was inserted into flame by FAAS with a magnetic probe. The limits of quantification (<4.6 µg L-1) were smaller than maximum residue limits established in Brazil. Good precisions and accuracies were obtained. DMSS-FAAS presented a sensitivity at least 14 times greater than the d-SPE followed by conventional FAAS analysis, wherein the analytes were extracted and desorbed, and the eluate was introduced in FAAS via nebulization system. Lead was easily quantified in juice samples at very low concentrations, with satisfactory figures of merit, and without the need of a mineralization step.

Outstanding Enrofloxacin Removal Using an Unmodified Low-Cost Sorbent Prepared from the Leaves of Pyracantha koidzumii.

Increasing discharges of synthetic antimicrobial agents from industrial and municipal sewage, as well as from agricultural runoffs into water bodies, is still a global challenge. Here, an unmodified low-cost sorbent was prepared in an ecofriendly manner from Pyracantha koidzumii leaves for the removal of enrofloxacin (ENR). Sorbent characterization was accomplished using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), BET surface area, zeta potential, and point of zero charge. Biosorption assays were carried out via batch mode concerning the impact of adsorbent dosage, contact time, solution pH, solution ionic strength, adsorbate concentration, and temperature. In general, ENR adsorption was significantly correlated with pH and ionic strength. At a neutral pH, the sorbent had a theoretical maximal ENR uptake of 138.89 mg/g. However, the adsorption capacity was significantly affected by the presence of high concentrations of divalent cations (Ca2+ and Mg2+). The findings from the kinetics and isotherms showed that the pseudo-second-order kinetic and Langmuir isotherm models best fit the experimental data. Electrostatic interactions, hydrogen bonding, and π-π stacking were the most important mechanisms of adsorption of ENR onto the P. koidzumii sorbent. Overall, this study suggests the promising application of this agricultural residue for the efficient removal of ENR from water.

Detection and quantification of prostaglandin E2 in saliva by liquid chromatography-tandem mass spectrometry using microextraction by packed sorbent.

The detection of eicosanoids in saliva samples can assist pharmacokinetic/pharmacodynamic studies due to the facility of obtaining samples, minimal discomfort and high adherence of volunteers to the study. The present study enabled determine prostaglandin E2 concentrations in saliva samples, using a microextraction by packed sorbent methodology and subsequent detection in liquid chromatography-tandem mass spectrometry. Twelve volunteers underwent scaling and coronary-radicular polishing of the upper molars and sequential saliva collections: 0.25-96 h after ingestion of a 600 mg ibuprofen tablet, to quantify prostaglandin E2 concentrations. There was an increase in the level of prostaglandin E2 with a significant difference after the dental procedure (0.25 h) compared to 11, 24, 48 and 72 h (*p < 0.05). After taking the drug, these levels begin to decrease up to 5 h, returning to normal in the subsequent hours. The method was developed and validated with linearity between 2.4 and 1250 ng/mL and r2 above 0.9932. The limit of quantitation was about 2.4 ng/mL. The coefficients of variation and the relative standard errors of the accuracy and precision analyzes were < 15%. The proposed extraction and analysis methodology proved to be efficient, fast and promising for pharmacokinetic/pharmacodynamic assays after using anti-inflammatory drugs.

Efficiency of the removal of tetraethyl pyrophosphate (TEPP) pesticide in water: use of cork granules as a natural adsorbent on acetylcholinesterase activity in neuronal PC12 cell.

Tetraethyl pyrophosphate (TEPP) is an organophosphate pesticide that irreversibly inhibits acetylcholinesterase (AChE). Cork powder or granules have been recommended as a sustainable sorbent to remove pesticides from water. In the present study, we evaluated the effectiveness of removing TEPP from water using wine corks to obtain cork granules as natural adsorbent, analyzing the TEPP effects on AChE activity in commercial enzyme from Electrophorus electricus and secreted by neuronal PC12 cells. TEPP inhibited AChE activity in a concentration-dependent manner. For the first time, we showed that different concentrations of TEPP diluted in water after adsorption experiments using cork granules decreased TEPP's inhibitory effects on AChE activity in commercial enzyme and neuronal PC12 cell culture medium. Our results suggest that the optimum removal of TEPP from water by corks was 91.4 ± 4.0%. Overall, the findings support the hypothesis that cork granules can be used to remediate pesticide-contaminated environments, such as those contaminated by organophosphate pesticides, and demonstrate a new application of a biochemical assay on AChE activity using a commercial enzyme or secreted by neuronal PC12 cells in culture as a possible methodologic strategy for evaluating the success of TEPP removal from water.

Nanosorbents as Materials for Extraction Processes of Environmental Contaminants and Others.

The aim of this work focuses on the application of nanomaterials (NMs) in different sorptive extraction techniques for the analysis of organic contaminants from environmental samples of distinct matrix compositions. Without any doubt, the integration of specific NMs such as carbonaceous nanomaterials, magnetic nanoparticles (MNPs), metal-organic frameworks (MOFs), silica nanoparticles, and ion-imprinted NPs with solid-phase extraction techniques counting d-SPE, solid-phase microextraction (SPME), and stir bar sorptive extraction (SBSE) impact on the improvements in analytical performance. The application of NMs as sorbents in the extraction of organic pollutants in environmental samples allows for providing better sensitivity, repeatability, reproducibility, and reusability.

Spent mushroom substrate is capable of physisorption-chemisorption of CO2.

No in-depth investigation exists on the feasibility of integrating hydrothermal carbonization (HTC) and pelletization into the process of making spent mushroom substrate (SMS), an agro-food residue from the commercial mushroom industry, into an adsorbent for post-combustion CO2 removal. Therefore, this study analyzed if it could be possible for systematically converting low-pressure hydrochars of various SMSs into carbon-adsorbing mini-capsules. Sources of SMS included paddy straw and achiote capsule shell from Pleurotus ostreatus; eucalyptus sawdust and grassy straw from Lentinula edodes; and compost containing peat or soil as casing layer from Agaricus subrufescens. The eucalyptus sawdust and grassy straw from L. edodes outperformed the other biomaterials in adsorbing CO2, and thus effectively encapsuled most of the gas, 8.25 mmol g-1 and 8.10 mmol g-1, respectively. They contained mostly hetero-atoms of O and N, requiring less unit energy to bind acidic molecules of CO2 at the alkaline sites. The amount of unit energy the pore-filling process demanded at 25 °C was 12.65 kJ mol-1, an attribute of self-sustaining and saleable physisorption. A negative 6.80 kJ mol-1 free energy validated both spontaneity and exothermal of biocarbons at steady-state atmosphere. The major findings and innovations of our study support utilizing SMS as an adsorbent as a carbon capture, storage and utilization networking. Our insights into the physisorption-chemisorption on SMS are timely and relevant to help manage the re-use of SMS, and thus bring the global mushroom industry closer to environmental sustainability and toward a lower carbon society and circular economy.

Microextraction by packed sorbent of selected pesticides in coffee samples employing ionic liquids supported on graphene nanosheets as extraction phase.

This paper describes the synthesis, characterization, and use of ionic liquids supported on silica, functionalized with graphene oxide through covalent bonding (ILz/Si@GO), as sorbents for microextraction by packed sorbent (MEPS). Seven selected pesticides (diazinon, heptachlor, aldrin, endrin, dieldrin, endosulfan, and methoxychlor), used for the prevention of pests in coffee crops, and endosulfan sulfate-an endosulfan metabolite-were selected for this study as model compounds for evaluating the sorbent performance of the synthesized materials in the MEPS device. The cycles of each of the stages were previously optimized through univariate experiments to carry out the extraction. The ILz/Si@GO phase was compared to other sorbents used in MEPS (GO, DVB-MMA, C4/SiO2, C8/SiO2, ILz/SiO2, and bare silica) and also with graphene functionalized through other methodologies, where ILz/Si@GO showed the best results. The material was characterized using a range of techniques. The selectivity of the sorbent material and its adsorption capacity were evaluated by gas chromatography coupled with tandem mass spectrometry. The precision and accuracy of the method showed a relative standard deviation lower than 10% and recoveries from 35 to 97%. Finally, the proposed method was employed for the determination of pesticide residues in coffee samples.

Use of Poly(vinyl alcohol)-Malic Acid (CLHPMA) Hydrogels and Chitosan Coated Calcium Alginate (CCCA) Microparticles as Potential Sorbent Phases for the Extraction and Quantitative Determination of Pesticides from Aqueous Solutions.

Pesticides are used worldwide to increase crop yields in agriculture. However, their toxicity and accumulation capacity can make them toxic to the environment, animals and humans. In the case of workers chronically exposed to these substances, they must be sampled continuously, so urine is an excellent option. In this sense, this study proposes to use poly(vinyl alcohol)-malic acid hydrogels, and chitosan-coated calcium alginate as new sorbent phases to be used in pesticide determination processes in urine. To better understand the behavior of these materials in the capture and desorption process, molecular dynamics simulations (MDS) were used, and desorption experiments were performed, using mechanical agitation, ultrasound, and pH variation in the desorption process, in order to optimize the parameters to obtain better recoveries. Under the optimal experimental conditions, the maximum recoveries were of the order of 11% (CFN), 3% (KCF), 53% (DMT), 18% (MTD) and 35% (MTL). Although the recoveries were not exhaustive, they are a first approximation for the use of these new sorbent phases in the determination of this type of compound in aqueous solutions and urine.

Self-supported 3D reduced graphene oxide for solid-phase extraction: An efficient and low-cost sorbent for environmental contaminants in aqueous solution.

A 3D reduced graphene oxide (3D-rGO), a self-supported, efficient, and low-cost sorbent, was synthesised and employed in a solid-phase extraction (SPE) cartridge. As a proof of concept, it was applied to remove diclofenac from aqueous solution. After applying statistical methods to systematically investigate key parameters for optimizing the 3D-rGO cartridge performance, it reached removal and elution efficiencies of 100 % and 90 %, respectively. This SPE cartridge presented advantages compared to traditional ones as the smaller amount of material into the cartridge (mass twenty times smaller), in addition to the ability of eliminating sorbent preconditioning, reducing the use of solvents, and making the process environmentally friendly with a faster operation. Also, it presented improved reproducibility after several cycles of reuse, and finally a lower cost of production unveiled by a cost-benefit analysis. Analysis with scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectrometry, Raman, and Fourier transform infrared spectroscopy in attenuated total reflectance mode suggested that the 3D framework morphology with a high content of carbon at the surface and some residual oxygen-containing groups are the protagonists in this performance. Therefore, 3D-rGO has the potential to be a highly efficient sorbent in analytical procedures using SPE for environmental contaminants in water and effluent samples.

A biotechnological tool for glycoprotein desialylation based on immobilized neuraminidase from Clostridium perfringens.

BACKGROUND: Sialic acids are widely distributed in nature and have biological relevance owing to their varied structural and functional roles. Immobilized neuraminidase can selectively remove terminal N-acetyl neuraminic acid from glycoproteins without altering the protein backbone while it can be easily removed from the reaction mixture avoiding sample contamination. This enables the evaluation of changes in glycoprotein performance upon desialylation. METHODS: Neuraminidase was immobilized onto agarose activated with cyanate ester groups and further used for desialylation of model glycoproteins, a lysate from tumour cells and tumour cells. Desialylation process was analysed by lectin binding assay, determination of sialyl-Tn or flow cytometry. RESULTS: Clostridium perfringens neuraminidase was immobilized with 91 % yield and expressed activity yield was of 41%. It was effective in the desialylation of bovine fetal serum fetuin, bovine lactoferrin and ovine submaxilar mucin. A decrease in sialic-specific SNA lectin recognition of 83% and 53 % was observed for fetuin and lactoferrin with a concomitant increase in galactose specific ECA and PNA lectin recognition. Likewise, a decrease in the recognition of a specific antibody (82%) upon mucin desialylation was observed. Moreover, desialylation of a protein lysate from the sialic acid-rich cell line TA3/Ha was also possible leading to a decrease in 47 % in SNA recognition. Immobilized neuraminidase kept 100% of its initial activity upon five desialylation cycles. CONCLUSIONS: Immobilized neuraminidase is an interesting as well as a robust biotechnological tool for enzymatic desialylation purposes. GENERAL SIGNIFICANCE: Immobilized neuraminidase would contribute to understand the role of sialic acid in biological processes.

Evaluation of the QuEChERS method for the determination of phenolic compounds in yellow (Brassica alba), brown (Brassica juncea), and black (Brassica nigra) mustard seeds.

Studies about the phenolic composition of yellow (Brassica alba), brown (Brassica juncea), and black (Brassica nigra) mustard seeds are still scarce in the literature. Hence, this study describes, for the first time, the use of the QuEChERS extraction method followed by UHPLC-MS/MS analysis for phenolic compound determination in the seeds of these mustard species. Under the optimized extraction and analysis conditions, twenty-one phenolic compounds were evaluated. Six, eleven, and seven were found in B. alba, B. juncea, and B. nigra seeds, respectively. The most abundant phenolic compound was sinapic acid, which was found in amounts ranging from 44 to 82 times higher than the other major compounds found in the mustard seeds, ferulic, 4-hydroxybenzoic and protocatechuic acids. Overall, these results are an important contribution to the characterization of the phenolic composition of the three in natura mustard seeds species, and support future reliable phenolic compounds determination with the QuEChERS method.

Mesoporous molecularly imprinted polymer core@shell hybrid silica nanoparticles as adsorbent in microextraction by packed sorbent for multiresidue determination of pesticides in apple juice.

In this work, we report the synthesis of a mesoporous molecularly imprinted polymer on the surface of silica nanoparticles (core@mMIP) to be applied as adsorbent in microextraction by packed sorbent (MEPS) for selective determination of pesticides in apple juice. The core@mMIP was properly characterized, showing good adhesion of the polymer to the silica core. The best extraction conditions were: 200 µL of ultrapure water as washing solvent, 150 µL of acetonitrile as eluent, 100 µL of sample at pH 2.5, five draw-eject cycles and 8 mg of adsorbent. Thereby, recoveries of 96.12 ± 1.05%, 76.88 ± 6.18% and 76.18 ± 5.57% were obtained for pyriproxyfen (PPX), deltamethrin (DTM) and etofenprox (ETF), respectively. After validation, the method presented linearity in the range of 0.02-10 µg mL-1 (r > 0.99), limit of detection of 0.005 µg mL-1, satisfactory selectivity, and proper precision and accuracy. The method was successfully applied real samples of processed and fresh apple juice.