Nanomaterials-based aptasensors: An efficient detection tool for heavy-metal and metalloid ions in environmental and biological samples.

In light of potential risks of heavy metal exposure, diverse aptasensors have been developed through the combination of aptamers with nanomaterials for the timely and efficient detection of metals in environmental and biological matrices. Aptamer-based sensors can benefit from multiple merits such as heightened sensitivity, facile production, uncomplicated operation, exceptional specificity, enhanced stability, low immunogenicity, and cost-effectiveness. This review highlights the detection capabilities of nanomaterial-based aptasensors for heavy-metal and metalloid ions based on their performance in terms of the basic quality assurance parameters (e.g., limit of detection, linear dynamic range, and response time). Out of covered studies, dendrimer/CdTe@CdS QDs-based ECL aptasensor was found as the most sensitive option with an LOD of 2.0 aM (atto-molar: 10-18 M) detection for Hg2+. The existing challenges in the nanomaterial-based aptasensors and their scientific solutions are also discussed.

Determination of alkylphenols, phenylphenols, bisphenol A, parabens, organophosphorus pesticides and triclosan in different cereal-based foodstuffs by gas chromatography-mass spectrometry.

The high toxicity of endocrine disrupting chemicals (EDCs) has promoted the development of effective techniques for their separation and detection in various types of matrices. In this work, we developed a method for the rapid, reliable determination of 24 EDCs from six different families of organic compounds (viz. alkylphenols, phenylphenols, bisphenol A, parabens, organophosphorus pesticides and triclosan) in cereal-based foodstuffs. The target compounds were subjected to ultrasound-assisted extraction with methanol, cleaned up and preconcentrated by automated solid-phase extraction, and derivatized for their determination by gas chromatography-mass spectrometry (GC-MS). The method features low limits of detection (0.4-23 ng/kg), good precision (3.8-7.2%) and recoveries from 82% to 105%. The proposed method was used to analyse 12 samples of products purchased in Andalusia (Spain). A total of 14 analytes were detected in most of the samples. In any case, their concentrations (3.8-620 ng/kg) were all lower than the applicable maximum residue limits.

A multi-residue method for GC-MS determination of selected endocrine disrupting chemicals in fish and seafood from European and North African markets.

An integrated study was conducted to determine the presence of six types of endocrine disrupting chemicals (bisphenol A, triclosan, two alkylphenols, two phenylphenols, eleven organophosphorus pesticides and seven parabens) in the fish and seafood samples from Europe and North Africa. The proposed method involves ultrasound-assisted extraction followed by continuous solid-phase extraction prior to GC-MS analysis. Analytical quality parameters such as linearity, accuracy, precision, sensitivity and selectivity were all good. Limits of detections ranged from 0.5 to 20.0 ng/kg. The relative standard deviation was lower than 7.5% and recoveries ranged from 84 to 105%. The method was successfully used to determine the target analytes in 20 fish and seafood samples from different fish shops and supermarkets in Europe and North Africa. Analyte contents spanned the range 4.6-730 ng/kg and were all below the maximum legally allowed limits. EDCs most frequently found in the samples analysed were dichlorvos, 2-phenylphenol and nonylphenol.

Use of semi-automated continuous solid-phase extraction and gas chromatography-mass spectrometry for the determination of polycyclic aromatic hydrocarbons in alcoholic and non-alcoholic drinks from Andalucía (Spain).

BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) are a large group of contaminants that can reach drinks in various ways. Their assessment in terms of food safety is needed as a priority. The present study developed a methodology to estimate their presence in several types of drinks. RESULTS: In this work, a method was developed for detecting and quantifying PAHs in drinks using a semi-automated, solid-phase extraction closed system for clean up and isolation, and gas chromatography-mass spectrometry (GC-MS) for determination. The proposed method is accurate, precise, and sensitive, with low limits of detection (0.02-0.6 ng L-1 ), low relative standard deviations (< 6.5%), and high recoveries (90-103%). Its high flexibility allows application to a variety of drinks from (Spain) including distillates, beer, wine, cider, soft drinks, fruit juice, tea, and coffee. CONCLUSION: This methodology allows the detection of this family of compounds at trace levels using low quantities of sample and solvents. Most of the samples studied contained two or more of the Environmental Protection Agency's (EPA's) 16 PAH priority pollutants, albeit at levels below the legally allowed limit. © 2018 Society of Chemical Industry.

Determination of 13 endocrine disrupting chemicals in environmental solid samples using microwave-assisted solvent extraction and continuous solid-phase extraction followed by gas chromatography-mass spectrometry.

Soil can contain large numbers of endocrine disrupting chemicals (EDCs). The varied physicochemical properties of EDCs constitute a great challenge to their determination in this type of environmental matrix. In this work, an analytical method was developed for the simultaneous determination of various classes of EDCs, including parabens, alkylphenols, phenylphenols, bisphenol A, and triclosan, in soils, sediments, and sewage sludge. The method uses microwave-assisted extraction (MAE) in combination with continuous solid-phase extraction for determination by gas chromatography-mass spectrometry. A systematic comparison of the MAE results with those of ultrasound-assisted and Soxhlet extraction showed MAE to provide the highest extraction efficiency (close to 100%) in the shortest extraction time (3 min). The proposed method provides a linear response over the range 2.0 - 5000 ng kg(-1) and features limits of detection from 0.5 to 4.5 ng kg(-1) depending on the properties of the EDC. The method was successfully applied to the determination of target compounds in agricultural soils, pond and river sediments, and sewage sludge. The sewage sludge samples were found to contain all target compounds except benzylparaben at concentration levels from 36 to 164 ng kg(-1). By contrast, the other types of samples contained fewer EDCs and at lower concentrations (5.6 - 84 ng kg(-1)).

Electrochemical and quantum chemical approaches to the study of dopamine sensing using bentonite and l-cysteine modified carbon paste electrode.

This work presents a significant investigation involving both electrochemical experiment and quantum chemical simulation approaches. The objective was to characterize the electrochemical detection of dopamine (DA). The detection was carried out using a modified carbon paste electrode (CPE) incorporating bentonite (Bent) and l-cysteine (CySH) (named as CySH/Bent/CPE). To understand and explain the oxidation mechanism of DA on the CySH/Bent modified electrode surface, the coupling of the two approaches were exploited. The CySH/Bent/CPE showed excellent electroactivity toward DA such as good sensibility, selectivity, stability, and regenerative ability. The developed sensor shows a dynamic linear range from 0.8 to 80 µM with a limit of detection and quantification of 0.5 µM and 1.5 µM, respectively. During the quantitative analysis of DA in presence of ascorbic acid (AA) and uric acid (UA) the electrochemical oxidation signals of AA, DA, and UA distinctly appear as three separate peaks. The potential differences between the peaks are 190 mv, 150 mv, and 340 mV for the AA-DA, DA-UA, and AA-UA oxidation pairs, respectively. These observations stem from square wave voltammetry (SWV) studies, along with the corresponding redox peak potential separations. The developed sensor is simple and accurate to monitor DA in human serum samples. On the other hand, CySH acts as an electrocatalyst on the CySH/Bent/CPE surface by increasing its active electron transfer sites, as suggested by the quantum chemical modeling with analytical results of Fukui. Furthermore, the voltammetric results obtained agree well with the theoretical calculations.

Graphene quantum dots based on cannabis seeds for efficient wound healing in a mouse incisional wound model: Link with stress and neurobehavioral effect.

Graphene quantum dots (GQDs) are promising biomaterials with potential applicability in several areas due to their many useful and unique features. Among different applications, GQDs are photodynamic therapy agents that generate single oxygen and improve antimicrobial activity. In the present study, and for the first time, GQD were isolated from the Cannabis sativa L. seeds to generate C-GQDs as a new biomaterial for antibacterial and wound healing applications. Detailed characterization was performed using FTIR, UV-vis, Raman spectra, photoluminescence, TEM examination, HRTEM, ζ-potential, and XRD. Our results revealed in vitro and in vivo antibacterial activity of C-GQDs against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) with reduced minimal inhibitory concentration of 236 µg/mL for both strains. In addition, the C-GQDs confirmed the in vitro analysis and exhibited anti-inflammatory activity by reducing the level of neutrophils in blood and skin tissue. C-GQDs act by accelerating re-epithelization and granulation tissue formation. In addition, C-GQDs restored neurobehavioral alteration induced by incisional wounds by reducing oxidative stress, decreasing cortisol levels, increasing anxiolytic-like effect, and increasing vertical locomotor activity. The wound-healing effects of C-GQDs support its role as a potential therapeutic agent for diverse skin injuries.

Advancements in nanomaterial-based aptasensors for the detection of emerging organic pollutants in environmental and biological samples.

The combination of nanomaterials (NMs) and aptamers into aptasensors enables highly specific and sensitive detection of diverse pollutants. The great potential of aptasensors is recognized for the detection of diverse emerging organic pollutants (EOPs) in different environmental and biological matrices. In addition to high sensitivity and selectivity, NM-based aptasensors have many other advantages such as portability, miniaturization, facile use, and affordability. This work showcases the recent advances achieved in the design and fabrication of NM-based aptasensors for monitoring EOPs (e.g., hormones, phenolic contaminants, pesticides, and pharmaceuticals). On the basis of their sensing mechanisms, the aptasensing systems can be classified as electrochemical, colorimetric, PEC, fluorescence, SERS, and ECL aptasensors. Special attention has been paid to the fabrication processes, analytical reliability, and sensing mechanisms of NM-based aptasensors. Further, the practical utility of aptasensing approaches has also been assessed based on their basic performance metrics (e.g., detection limits, sensing ranges, and response times).

Fe3O4@UiO-66-NH2 based on magnetic solid phase extraction for determination of organic UV filters in environmental water samples.

In this work, a nanocomposite structured magnetic metal-organic framework named as Fe3O4@UiO-66-NH2 was prepared via a simple hydrothermal approach. The as-mentioned nanocomposite was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and the Brunauer-Emmett-Teller (BET) techniques. Using the Fe3O4@UiO-66-NH2 as a nanosorbent, an easy and highly effective approach was developed to preconcentrate nine organic UV filters before gas chromatography-mass spectrometry (GC-MS) analysis. Different conditions influencing the extraction efficiency encompassing the sorbent amount, nature and volume of desorption solvent, desorption time, pH of the sample, and extraction time, were examined. Under the optimal experimental parameters, the Fe3O4@UiO-66-NH2-based magnetic solid phase extraction and GC-MS (MSPE-GC-MS) demonstrated linearity in the range of 0.03-1500 ng/L (R2 ≥ 0.9974) and the reproducibility, expressed as RSD, was ≤7.5%. The limits of detection ranged between 0.01 and 0.07 ng/L and limits of quantification were in the range of 0.03-0.4 ng/L. Finally, the suggested approach was satisfactorily utilized to determine nine organic UV filters in different water samples (analytical recoveries between 86.5% and 104.2%).

Ultrasound-assisted adsorption of organic dyes in real water samples using zirconium (IV)-based metal-organic frameworks UiO-66-NH2 as an adsorbent.

The utilization of dye adsorption through metal-organic frameworks represents an eco-friendly and highly effective approach in real water treatment. Here, ultrasound assisted adsorption approach was employed for the remediation of three dyes including methylene blue (MB), malachite green (MG), and congo red (CR) from real water samples using zirconium(IV)-based adsorbent (UiO-66-NH2). The adsorbent was characterized for structural, elemental, thermal and morphological features through XRD, XPS, FTIR, thermogravimetric analysis, SEM, BET , and Raman spectroscopy. The adsorption capacity of adsorbent to uptake the pollutants in aqueous solutions was investigated under different experimental conditions such as amount of UiO-66-NH2 at various contact durations, temperatures, pH levels, and initial dye loading amounts. The maximum removal of dyes under optimal conditions was found to be 938, 587, and 623 mg g-1 towardMB, MG, and CR, respectively. The adsorption of the studied dyes on the adsorbent surface was found to be a monolayer and endothermic process. The probable mechanism for the adsorption was chemisorption and follows pseudo-second-order kinetics. From the findings of regeneration studies, it was deduced that the adsorbent can be effectively used for three consecutive cycles without any momentous loss in its adsorption efficacy. Furthermore, UiO-66-NH2 with ultrasound-assisted adsorption might help to safeguard the environment and to develop new strategies for sustainability of natural resources.

Effects of graphene oxide nanoparticles administration against reserpine-induced neurobehavioral damage and oxidative stress in an animal model of Parkinson's disease.

Parkinson's disease (PD) is a progressive neurodegenerative disease characterized by the degeneration of substantia nigra dopaminergic neurons. Many therapeutic strategies were explored for PD with no success. In this study, we investigated the efficacy of graphene oxide nanoparticles (GONPs) using the reserpine model of PD. Low concentrations GONPs were utilized as a therapeutic agent in many neurodegenerative diseases. We assessed the neurobehavioral alterations in the reserpine model of PD and investigated the neuroprotective and antioxidant effects of GONPs in this model. Thirty male mice were separated into three groups (N = 10): C (control); Res (Reserpine 0.25 mg/kg); Res + GONPs (Reserpine 0.25 mg/kg and GONPs 25 mg/kg). Our results showed that reserpine neurotoxicity induced hypoactivity with a significant increase of superoxide dismutase (SOD), catalase (CAT), and malondialdehyde (MDA) levels in the brain and brainstem. GONPs reversed the reserpine-induced hypoactivity concomitant with decreased neuronal CAT and MDA levels. These findings support the potential use of GONPs as an antioxidant agent in the central nervous system (CNS) that protects against neurodegeneration in the reserpine PD model.

Occurrence and distribution of endocrine disrupting chemicals and pharmaceuticals in the river Bouregreg (Rabat, Morocco).

In this work, Moroccan surface waters were analysed for 27 endocrine disrupting chemicals and pharmaceutically active compounds. The study area was selected on the grounds of the scarcity of information about the contamination status of rivers in the Rabat region, which receive micropollutants from municipal and industrial wastewater, and runoff from agricultural fields. In fact, animal feed residues, urban water runoff and untreated waste discharges into old landfills reach river water in an area with a population of ca. 3 752 800 where more than 99% of all drinking water is obtained from surface water. Samples were collected at five different sites upstream and downstream the river Bouregreg and the target compounds determined by using a continuous solid-phase extraction system and gas chromatography-mass spectrometry. Unlike the pharmaceuticals, most of the EDCs (specifically, 4-tert-octylphenol, nonylphenol, 4-phenylphenol, 2-phenylphenol, estrone, 17ß-estradiol, triclosan and bisphenol A) were present in all samples with detection frequencies above 68%, the highest concentrations (142-368 ng/L) being those at the river mouth. The pharmaceuticals found encompassed five therapeutic classes and their concentrations ranged from 2.5 to 351 ng/L. Overall, the most abundant class were the anti-inflammatory/analgesic drugs with high detection frequencies (80%), followed by antibiotics and anti-epileptics (64%), lipid regulators (56%) and ß-blockers (12%). Based on the principal component analysis, the distribution of the emerging contaminants studied among sampling sites was consistent with the physico-chemical properties of the water, the most heavily contaminated sites being those close to the mouth of the river.

Advances in surface plasmon resonance-based biosensor technologies for cancer biomarker detection.

Surface plasmon resonance approach is a highly useful option to offer optical and label-free detection of target bioanalytes with numerous advantages (e.g., low-cost fabrication, appreciable sensitivity, label-free detection, and outstanding accuracy). As such, it allows early diagnosis of cancer biomarkers to monitor tumor progression and to prevent the recurrence of oncogenic tumors. This work highlights the recent progress in SPR biosensing technology for the diagnosis of various cancer types (e.g., lung, breast, prostate, and ovarian). Further, the performance of various SPR biosensors is also evaluated in terms of the basic quality assurance criteria (e.g., limit of detection (LOD), selectivity, sensor response time, and reusability). Finally, the limitations and future challenges associated with SPR biosensors are also discussed with respect to cancer biomarker detection.

Nanomaterial-based aptasensors as an efficient substitute for cardiovascular disease diagnosis: Future of smart biosensors.

As a major cause of deaths in developed countries, cardiovascular disease (CVD) has been a big burden for human health systems. Its early and rapid detection is crucial to efficiently apply appropriate on time therapy and to ultimately reduce the associated mortality rate. Aptamers, known as single-stranded DNA/RNA or oligonucleotides containing receptors and/or catalytic properties, have been widely employed in biodetection platforms due to their beneficial properties. Like antibodies, aptamers have served as artificial target receptors in affinity biosensors. Currently, advanced biosensors with improved sensitivity and specificity are fabricated by the synergistic combination of aptamers and diverse nanomaterials. Herein, we review the current development and applications of nanomaterial-based aptasensors for the recognition of CVD biomarkers with special emphasis on electrochemical and optical technologies. The performance of aptasensors has been assessed further in terms of key quality assurance metrics along with discussions on recent technologies developed for the amplification of signals with enhanced portability.

A multi-residue method for determining twenty-four endocrine disrupting chemicals in vegetables and fruits using ultrasound-assisted solid-liquid extraction and continuous solid-phase extraction.

In this work, we developed an analytical approach using an ultrasound-assisted extraction (UAE) followed by continuous solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) detection in order to determine simultaneously 24 endocrine disrupting chemicals such as alkylphenols, organophosphorus pesticides, parabens, phenylphenols, triclosan and bisphenol A in vegetable and fruit samples. Different variables influencing UAE and SPE performance were optimized in order to maximize removal of the sample matrix and preconcentration of the analytes. The optimized extraction and GC-MS quantitation conditions provided acceptable sensitivity, selectivity, accuracy and precision. Limits of detection spanned the range 0.6-25 ng kg-1, recoveries were near-quantitative and relative standard deviations ranged from 4.5 to 7.6%. The proposed method was used to analyse 11 vegetable samples and 7 fruit samples purchased at various Spanish and Moroccan supermarkets. Most samples contained more than three of the analytes, at levels between 5.8 and 580 ng kg-1.

Validation and Use of an Accurate, Sensitive Method for Sample Preparation and Gas Chromatography-Mass Spectrometry Determination of Different Endocrine-Disrupting Chemicals in Dairy Products.

Endocrine disrupting chemicals (EDCs) are exogenous substances capable of altering the human hormone system and causing various diseases such as infertility and cancer as a result. In this work, a method for determining twenty-three different EDCs including parabens, alkylphenols, phenylphenols, organophosphorus pesticides, bisphenol A and triclosan in dairy products was developed. Samples are conditioned by addition of acetonitrile containing 1% formic acid, centrifugation and clean-up of the extract by continuous solid-phase extraction. EDCs in the extract are derivatised by heating in a microwave oven and quantified by gas chromatography-mass spectrometry. The proposed method features good limits of detection (6-40 ng/kg) and precision (relative standard deviation < 7.6%); also, it is scarcely subject to matrix effects (1-20%). EDC recoveries from spiked samples ranged from 80 to 108%. The method was used to analyse a total of 33 samples of dairy products including cow, sheep and goat milk, yoghourt, milkshakes, cheese, cream, butter and custard. Bisphenol A was the individual contaminant detected in the greatest number of samples, at concentrations from 180 to 4800 ng/kg. 2-Phenylphenol and ethylparaben were found in more than one-half, at concentrations over the range 130-3500 and 89-4300 ng/kg, respectively. In contrast, alkylphenols, organophosphorus pesticides and triclosan were detected in none.

Recent progress in nanomaterial-based sensing of airborne viral and bacterial pathogens.

Airborne pathogens are small microbes that can cause a multitude of diseases (e.g., the common cold, flu, asthma, anthrax, tuberculosis, botulism, and pneumonia). As pathogens are transmitted from infected hosts via a number of routes (e.g., aerosolization, sneezing, and coughing), there is a great demand to accurately monitor their presence and behavior. Despite such need, conventional detection methods (e.g., colony counting, immunoassays, and various molecular techniques) generally suffer from a number of demerits (e.g., complex, time-consuming, and labor-intensive nature). To help overcome such limitations, nanomaterial-based biosensors have evolved as alternative candidates to realize portable, rapid, facile, and direct on-site identification of target microbes. In this review, nano-biosensors developed for the detection of airborne pathogens are listed and discussed in reference to conventional options. The prospects for the development of advanced nano-biosensors with enhanced accuracy and portability are also discussed.

Recent Advances in Monitoring, Sampling, and Sensing Techniques for Bioaerosols in the Atmosphere.

Bioaerosols in the form of microscopic airborne particles pose pervasive risks to humans and livestock. As either fully active components (e.g., viruses, bacteria, and fungi) or as whole or part of inactive fragments, they are among the least investigated pollutants in nature. Their identification and quantification are essential to addressing related dangers and to establishing proper exposure thresholds. However, difficulties in the development (and selection) of detection techniques and an associated lack of standardized procedures make the sensing of bioaerosols challenging. Through a comprehensive literature search, this review examines the mechanisms of conventional and advanced bioaerosol detection methods. It also provides a roadmap for future research and development in the selection of suitable methodologies for bioaerosol detection. The development of sample collection and sensing technology make it possible for continuous and automated operation. However, intensive efforts should be put to overcome the limitations of current technology as most of the currently available options tend to suffer from lengthy sample acquisition times and/or nonspecificity of probe material.

Isolation and determination of ivermectin in post-mortem and in vivo tissues of dung beetles using a continuous solid phase extraction method followed by LC-ESI+-MS/MS.

A new analytical method based on solvent extraction, followed by continuous solid-phase extraction (SPE) clean-up using a polymeric sorbent, was demonstrated to be applicable for the detection of ivermectin in complex biological matrices of dung beetles (hemolymph, excreta or dry tissues) using liquid chromatography combined with positive electrospray ionization tandem mass spectrometry (LC/ESI+-MS/MS). Using a signal-to-noise ratio of 3:1, the limit of detection (LOD) in the insect matrices at trace levels was 0.01 ng g-1 and the limit of quantification (LOQ) was 0.1 ng g-1. The proposed method was successfully used to quantitatively determine the levels of ivermectin in the analysis of small samples in in vivo and post mortem samples, demonstrating the usefulness for quantitative analyses that are focused on future pharmacokinetic and bioavailability studies in insects and the establishment of a new protocol to study the impact of ivermectin on non-target arthropods such as dung beetles and other insects that are related with the "dung community". Because satisfactory precision and accuracy values were obtained in both in vivo matrices, we suggest that the method can be consistently used for quantitative determinations that are focused on future pharmacokinetic and bioavailability studies in insects. Furthermore, this new analytical method was successfully applied to biological samples of dead dung beetles from the field suggesting that the method can be used to establish a new routine analysis of ivermectin residues in insect carcasses that is applied to complement typical mortality tests.

Simultaneous determination of parabens, alkylphenols, phenylphenols, bisphenol A and triclosan in human urine, blood and breast milk by continuous solid-phase extraction and gas chromatography-mass spectrometry.

A highly sensitive gas chromatography-mass spectrometry (GC-MS) method for the determination of endocrine disrupting chemicals (EDCs) including parabens, alkylphenols, phenylphenols, bisphenol A and triclosan in human breast milk, blood and urine samples is proposed. Blood and milk require a pretreatment to remove proteins and other substances potentially interfering with the continuous solid-phase extraction (SPE) system used; on the other hand, urine samples can be directly introduced into the system after filtering. Analytes are retained on a LiChrolut EN column and derivatized by silylation following elution with acetonitrile. The resulting trimethylsilyl derivatives are determined by GC-MS. The proposed method exhibited good linearity (r(2)>0.995) for all target EDCs over the concentration range 0.7-10,000ng/l in urine, and 3.3-50,000ng/l in blood and milk. Also, it provided low limits of detection (0.2-1.8ng/l in urine, and 1.0-9.0ng/l in blood and milk), good precision (relative standard deviations less than 7%) and recoveries from 86 to 104%. A total of 24 human fluid samples were analyzed and most found to contain some target EDC at concentrations from 0.10 to 14µg/l.