Volatile sulfur compounds in asthmatic children and adolescents: A cross-sectional study in breath and saliva.

BACKGROUND: Halitosis in children implies psychosocial repercussions. Risk factors associated with this condition are unclear, and detection methods are inaccurate. AIM: To quantify the levels of sulfur-like compounds in children with asthma and healthy children from a novel validated assay, and to establish the risk factors related to halitosis. DESIGN: One hundred and twenty-eight individuals (63 healthy and 65 asthmatic) from 3 to 17 years of age were tested using a passive colorimetric sensor to measure the levels of sulfur-like compounds in breath and saliva. Information was collected on oral hygiene habits, gingival and dental health, breathing type, and dental malocclusion. RESULTS: The mean values of hydrogen sulfide were 4.0 ± 6.8 and 19.7 ± 12.2 ppbv (parts per billion in volume) in the control and asthmatic groups, respectively (p < .001). The presence of higher concentrations of sulfur compounds was significantly associated (p < .05) with the presence of gingival inflammation, tongue coating, dental plaque, mouth breathing, hypomineralization, age, tongue brushing, and the use of dental floss. CONCLUSION: The level of sulfur in breath and saliva was significantly higher in patients with asthma. These results can serve as a precedent to raise awareness among paediatricians and parents about oral hygiene care in children and adolescents.

Isolation of Carbon Black from Soils by Dispersion for Analysis: Quantitation and Characterization by Field Flow Fractionation Techniques.

In the present work, a procedure based on a dispersive medium for carbon black (CB) isolation from soil samples for analysis was proposed for the first time. Polymeric and biological dispersants and a sequential use of both dispersants were assayed. Asymmetrical flow field flow fractionation with dynamic light scattering detector (AF4-DLS) and sedimentation field flow fractionation with multi-angle light scattering detector (SdF3-MALS) were used for CB quantitation and characterization in the achieved dispersions. Soil samples contaminated with CB were processed, and CB isolation depended on the solid size distribution and composition and dispersant nature. More quantitative isolations were achieved for the four soils treated by the biological dispersant. As the organic matter percentage is higher in soil, the CB isolation was better, varying between 75 and 99% with standard deviation (s) ⩽ 2% for all soils. A soil contaminated with a CB-based pigment paste was analyzed, achieving (99 ± 2)% expressed as expanded uncertainty (K = 2) of dispersive isolation by the biological dispersant, and the sampling was scaled to 250 g of soil with positive results. The procedure was completed by CB recovery to obtain a solid residue able to be reused if necessary. For the filter-aided recovery step, different membranes (fiberglass, nylon, and Teflon) with a pore size between 0.1 and 5 µm were tested. The quantitation of the CB retained in the filter was measured by diffuse reflectance spectroscopy. Teflon (0.10 µm) provided better results for CB recovery, and its re-dispersion was also studied with suitable results. Determination of CB from the filters by diffuse reflectance spectrometry provided the same results than AF4 for CB dispersions.

Determination of antioxidant activity by in situ synthesis of AgNPs using in-tube SPME coupled on-line to capillary liquid chromatography.

A chromatographic system based on in-tube SPME coupled to capillary LC-DAD has been used to study the synthesis of silver nanoparticles using polyphenols in different scenarios: excess of the reducing agent or of the silver salt, addition of the cationic surfactants, and thermal synthesis. The optimized synthesis conditions allowed to quantify the polyphenols used as reducing agents, such as Trolox and chlorogenic acid. Two chromatographic peaks with different absorption spectrum were monitored during the syntheses. Depending on the molar relationship, a linear relation between the area of the chromatographic peaks and the concentration of the silver or polyphenol was established. For stabilization of silver nanoparticles, different cationic surfactants were used allowing to evaluate the role of anion (chloride and bromide) and of the alkyl chain. The proposed methodology can be used to determine chlorogenic acid up to 3 mM with a detection limit of 34 µM at λ= 400 nm. Chlorogenic acid was determined in dietary products with successful results. Precision (RSD=10%) and recovery (97-100%) were also satisfactory.

A Colorimetric Method for the Rapid Estimation of the Total Cannabinoid Content in Cannabis Samples.

A colorimetric method for the estimation of the total content of cannabinoids in cannabis samples is proposed. The assay is based on the reaction of these compounds with the reagent Fast Blue B (FBB), which has been immobilized into polydimethylsiloxane (PDMS). The reaction and detection conditions have been established according to the results obtained for the individual cannabinoids Δ9-tetrahydrocannabidiol (THC), cannabidiol (CBD), and cannabinol (CBN), as well as for ethanolic extracts obtained from cannabis samples after ultrasonication. In contact with the extract and under basic conditions, the reagent diffuses from the PDMS device, producing a red-brown solution. The absorbances measured at 500 nm after only 1 min of exposure to the FBB/PDMS composites led to responses proportional to the amounts of the cannabinoids in the reaction media. Those absorbances have been then transformed in total cannabinoid content using CBD as a reference compound. The potential utility of the proposed conditions has been tested by analyzing different cannabis samples. The selectivity towards other plants and drugs has been also evaluated. The present method is proposed as a simple and rapid alternative to chromatographic methods for the estimation of the total content of cannabinoids.

On-Site Multisample Determination of Chlorogenic Acid in Green Coffee by Chemiluminiscent Imaging.

The potential of antioxidants in preventing several diseases has attracted great attention in recent years. Indeed, these products are part of a multi-billion industry. However, there is a lack of scientific information about safety, quality, doses, and changes over time. In the present work, a simple multisample methodology based on chemiluminiscent imaging to determine chlorogenic acid (CHLA) in green coffee samples has been proposed. The multi-chemiluminiscent response was obtained after a luminol-persulfate reaction at pH 10.8 in a multiplate followed by image capture with a charge-coupled device (CCD) camera as a readout system. The chemiluminiscent image was used as an analytical response by measuring the luminescent intensity at 0 °C with the CCD camera. Under the optimal conditions, the detection limit was 20 µM and precision was also adequate with RSD < 12%. The accuracy of the proposed system was evaluated by studying the matrix effect, using a standard addition method. Recoveries of chlorogenic acid ranged from 93-94%. The use of the CCD camera demonstrated advantages such as analysis by image inspection, portability, and easy-handling which is of particular relevance in the application for quality control in industries. Furthermore, multisample analysis was allowed by one single image saving time, energy, and cost. The proposed methodology is a promising sustainable analytical tool for quality control to ensure green coffee safety through dosage control and proper labelling preventing potential frauds.

Reliable assessment of carbon black nanomaterial of a variety of cell culture media for in vitro toxicity assays by asymmetrical flow field-flow fractionation.

Carbon black nanomaterial (CB-NM), as an industrial product with a large number of applications, poses a high risk of exposure, and its impact on health needs to be assessed. The most common testing platform for engineered (E)NMs is in vitro toxicity assessment, which requires prior ENM dispersion, stabilization, and characterization in cell culture media. Here, asymmetric flow field-flow fractionation (AF4) coupled to UV-Vis and dynamic light scattering (DLS) detectors in series was used for the study of CB dispersions in cell culture media, optimizing instrumental variables and working conditions. It was possible to disperse CB in a non-ionic surfactant aqueous solution due to the steric effect provided by surfactant molecules attached on the CB surface which prevented agglomeration. The protection provided by the surfactant or by culture media alone was insufficient to ensure good dispersion stability needed for carrying out in vitro toxicity studies. On the other hand, cell culture media in combination with the surfactant improved dispersion stability considerably, enabling the generation of shorter particles and a more favourable zeta potential magnitude, leading to greater stability due to electrostatic repulsion. It was demonstrated that the presence of amino acids in the culture media improved the monodisperse nature and stability of the CB dispersions, and resulted in a turn towards more negative zeta potential values when the pH was above the amino acid isoelectric point (IEP). Culture media used in real cell culture scenarios were also tested, and in vitro toxicity assays were developed optimizing the compatible amount of surfactant.

Hand-Portable Miniaturized Liquid Chromatography for the Determination of Chlorogenic Acids in Dietary Supplements.

With the explosive growth of the dietary supplements industry, new demands have emerged that cannot be faced with the sophisticated instrumentation available in well-equipped laboratories. In particular, there is a demand for simplified and easy-to-use instruments, capable of providing results in short times of analysis. In this study, a hand-portable miniaturized liquid chromatograph (portable LC) has been tested for the determination of chlorogenic acids (CGAs) in products intended to supplement the diet and elaborated with green coffee extracts. CGAs offer several health benefits due to their antioxidant properties, and an increasing number of dietary supplements are marketed with claimed high contents of these compounds. The results obtained with the proposed portable LC approach have been compared with those obtained with two other miniaturized benchtop liquid chromatography instruments, namely, a capillary liquid chromatograph (capLC) and a nano liquid chromatograph (nanoLC). Although compared with the methods that used the benchtop instruments, the sensitivity attainable was lower, the portable LC instrument provided a comparable analytical performance for the quantification of the main GCAs at low mg g-1 levels, and it was clearly superior in terms of speed. The proposed portable LC-based method can be applied to assess the content and distribution profile of the predominant CGAs in this kind of dietary supplement. It can be also used to estimate the antioxidant power due to CGAs, as well as their preservation state.

Advances in the Measurement of Polymeric Colorimetric Sensors Using Portable Instrumentation: Testing the Light Influence.

Sustainable and green sensors based on polydimethyl siloxane (PDMS) or cellulose polymers, as a case of study of the use of portable instrumentation joined to a smartphone, have been tested. A smartphone camera was used to obtain images and was also coupled to a minispectrometer, without and with an optical fiber probe to register spectra. To study light influence on the analytical signal, light-emitting diode (LED), halogen light and daylight have been assayed. A corrective palette of 24 colors and a set with 45 colors from different color ranges were used as the validation set. The results indicated that halogen light was the best option to obtain the spectra. However, for digital image analysis, it was the LED light that gave a greater approximation of the RGB values of the real colors. Based on these results, the spectra and the RGB components of PDMS solid sensors doped with 1,2-naphtoquinone-4-sulfonate (NQS) for the determination of ammonium in water or urea in urine, PDMS doped with Griess reagent for developing the assay of nitrite in waters and cellulose sensors for the determination of hydrogen sulfide in the atmospheres have been obtained. The results achieved were good in terms of sensitivity and linearity and were comparable to those obtained using a laboratory benchtop instrument. Several rules for selecting the most suitable light source to obtain the spectra and/or images have been established and an image correction method has been introduced.

Improving Sustainability of the Griess Reaction by Reagent Stabilization on PDMS Membranes and ZnNPs as Reductor of Nitrates: Application to Different Water Samples.

A new approach based on the use of polydimethylsiloxane (PDMS) membranes doped with Griess reagents for in situ determination of NO2- and NO3-- in real samples is proposed. The influence of some doping compounds, on the properties of the PDMS membranes, such as tetraethyl orthosilicate (TEOS), or/and ionic liquids (OMIM PF6) has been studied. Membrane characterization was performed. To apply the procedure to NO3- determination, dispersed Zn nanoparticles (ZnNPs) were employed. The analytical responses were the absorbance or the RGB components from digital images. Good precision (RSD < 8%) and detection limit of 0.01 and 0.5 mgL-1 for NO2- and NO3-, respectively, were achieved. The approach was satisfactory when applied to the determination of NO2- and NO3- in drinking waters, irrigation and river waters, and waters from canned and fresh vegetables. The results obtained were statistically comparable with those by using nitrate ISE or UV measurement. This approach was transferred satisfactory to 96 wells for multianalysis. This study enables the improvement in the on-site determination of NO2- and NO3- in several matrices. It is a sustainable alternative over the reagent derivatizations in solution and presents several advantages such as being versatile, simplicity, low analysis time, cost, and energy efficiency. The response can be detected visually or by portable instruments such as smartphone.

Combining high performance thin layer chromatography with minispectrometer-fiber optic probe-coupled to smartphone for in place analysis: Lactose quantification in several matrices.

An in place colorimetric method has been proposed for estimation of the quantity of lactose in several matrix (milk, water effluents and surfaces). Analyzing the amount of this carbohydrate it can be control the product, the cleanliness of the parts of the dairy companies and it can avoid contamination of milk products produced there. This method combines the use of HPTLC for sugars separation with novel analytical devices as minispectrophotometer with fiber optic coupled to a smartphone. In order to measure the lactose a colorimetric reaction has been used. Variable volumes of samples or stock solutions were deposited in nano-silica gel layer, a mobile phase of acetonitrile:water:acetic acid was used for carbohydrate separation and a solution of thymol (0.05 g Thymol in 95 mL of EtOH and 5 mL H2SO4) was used for revealed the carbohydrate spot. Finally, the reflectance of samples and stock solutions were measured. The achieved limits of detection were 0.03 mg mL-1 and 0.003 mg mL-1 for the working concentration range and the analysis at traces level respectively.

Characterization and Quantitation of Carbon Black Nanomaterials in Polymeric and Biological Aqueous Dispersants by Asymmetrical Flow Field Flow Fractionation.

Characterization of carbon black (CB) nanomaterials is required in industrial and research areas. Hence, in this study, asymmetrical flow field flow fractionation coupled to UV-vis and DLS detectors in series (AF4-UV-vis-DLS) was studied to evaluate the CB dispersion behavior in polymeric and biological dispersants, given the relevance of these media in practical applications. Under the experimental conditions, the results indicated that polymeric and biological dispersions showed size distributions with hydrodynamic diameters of 404 and 175 nm, respectively, for a particle core diameter of 40 nm. The polymeric dispersant provided lower stability as a function of time than that achieved by the biological dispersant. AF4 allowed separation of different core-sized CB (40, 69, and 72 nm) according to their hydrodynamic size using cross-flow rates of 0.5 mL·min-1 and 1 mL·min-1 for polymeric and biological dispersants, respectively. The dilution of the polymeric dispersion with different real water matrices produced a dramatic loss of dispersion stability, this effect being negligible in the case of biological dispersions.

A Colorimetric Membrane-Based Sensor with Improved Selectivity towards Amphetamine.

Due to their simplicity, speed and low cost, chemical spot tests are increasingly demanded for the presumptive identification of illicit drugs in a variety of contexts such as point-of-care assistance or prosecution of drug trafficking. However, most of the colorimetric reactions used in these tests are, at best, drug class selective. Therefore, the development of tests based on chemical reactions with improved discrimination power is of great interest. In this work, we propose a new colorimetric assay for amphetamine (AMP) based on its reaction with solutions of alkaline gold bromide to form an insoluble yellow-orange derivative. The resulting suspensions are then filtered onto nylon membranes and the precipitate collected is used for the visual identification of AMP. The measurement of the absorbance of the membranes by diffuse reflectance spectroscopy also allows the quantification of AMP in a simple and rapid way, as demonstrated for different synthetic and drug street samples. On the basis of the results obtained, it was concluded that the proposed procedure is highly selective towards AMP, as this compound could be easily differentiated from other common drugs such as methamphetamine (MET), ephedrine (EPH), scopolamine (SCP) and cocaine (COC).

Capillary Liquid Chromatography for the Determination of Terpenes in Botanical Dietary Supplements.

Dietary supplements of botanical origin are increasingly consumed due to their content of plant constituents with potential benefits on health and wellness. Among those constituents, terpenes are gaining attention because of their diverse biological activities (anti-inflammatory, antibacterial, geroprotective, and others). While most of the existing analytical methods have focused on establishing the terpenic fingerprint of some plants, typically by gas chromatography, methods capable of quantifying representative terpenes in herbal preparations and dietary supplements with combined high sensitivity and precision, simplicity, and high throughput are still necessary. In this study, we have explored the utility of capillary liquid chromatography (CapLC) with diode array detection (DAD) for the determination of different terpenes, namely limonene, linalool, farnesene, α-pinene, and myrcene. An innovative method is proposed that can be applied to quantify the targets at concentration levels as low as 0.006 mg per gram of sample with satisfactory precision, and a total analysis time <30 min per sample. The reliability of the proposed method has been tested by analyzing different dietary supplements of botanical origin, namely three green coffee extract-based products, two fat burnings containing Citrus aurantium (bitter orange), and an herbal preparation containing lime and leaves of orange trees.

Corneal Biomechanical Parameters and Central Corneal Thickness in Glaucoma Patients, Glaucoma Suspects, and a Healthy Population.

PURPOSE: To evaluate and compare corneal hysteresis (CH), corneal resistance factor (CRF), and central corneal thickness (CCT), measurements were taken between a healthy population (controls), patients diagnosed with glaucoma (DG), and glaucoma suspect patients due to ocular hypertension (OHT), family history of glaucoma (FHG), or glaucoma-like optic discs (GLD). Additionally, Goldmann-correlated intraocular pressure (IOPg) and corneal-compensated IOP (IOPcc) were compared between the different groups of patients. METHODS: In this prospective analytical-observational study, a total of 1065 patients (one eye of each) were recruited to undergo Ocular Response Analyzer (ORA) testing, ultrasound pachymetry, and clinical examination. Corneal biomechanical parameters (CH, CRF), CCT, IOPg, and IOPcc were measured in the control group (n = 574) and the other groups: DG (n = 147), FHG (n = 78), GLD (n = 90), and OHT (n = 176). We performed a variance analysis (ANOVA) for all the dependent variables according to the different diagnostic categories with multiple comparisons to identify the differences between the diagnostic categories, deeming p < 0.05 as statistically significant. RESULTS: The mean CH in the DG group (9.69 mmHg) was significantly lower compared to controls (10.75 mmHg; mean difference 1.05, p < 0.001), FHG (10.70 mmHg; mean difference 1.00, p < 0.05), GLD (10.63 mmHg; mean difference 0.93, p < 0.05) and OHT (10.54 mmHg; mean difference 0.84, p < 0.05). No glaucoma suspects (FHG, GLD, OHT groups) presented significant differences between themselves and the control group (p = 1.00). No statistically significant differences were found in the mean CRF between DG (11.18 mmHg) and the control group (10.75 mmHg; mean difference 0.42, p = 0.40). The FHG and OHT groups showed significantly higher mean CRF values (12.32 and 12.41 mmHg, respectively) than the DG group (11.18 mmHg), with mean differences of 1.13 (p < 0.05) and 1.22 (p < 0.001), respectively. No statistically significant differences were found in CCT in the analysis between DG (562 µ) and the other groups (control = 556 µ, FHG = 576 µ, GLD = 569 µ, OHT = 570 µ). The means of IOPg and IOPcc values were higher in the DG patient and suspect groups than in the control group, with statistically significant differences in all groups (p < 0.001). CONCLUSION: This study presents corneal biomechanical values (CH, CRF), CCT, IOPg, and IOPcc for diagnosed glaucoma patients, three suspected glaucoma groups, and a healthy population, using the ORA. Mean CH values were markedly lower in the DG group (diagnosed with glaucoma damage) compared to the other groups. No significant difference was found in CCT between the DG and control groups. Unexpectedly, CRF showed higher values in all groups than in the control group, but the difference was only statistically significant in the suspect groups (FHG, GLD, and OHT), not in the DG group.

NQS-Doped PDMS Solid Sensor: From Water Matrix to Urine Enzymatic Application.

The development of in situ analytical devices has gained outstanding scientific interest. A solid sensing membrane composed of 1,2-naphthoquinone-4-sulfonate (NQS) derivatizing reagent embedded into a polymeric polydimethylsiloxane (PDMS) composite was proposed for in situ ammonium (NH4+) and urea (NH2CONH2) analysis in water and urine samples, respectively. Satisfactory strategies were also applied for urease-catalyzed hydrolysis of urea, either in solution or glass-supported urease immobilization. Using diffuse reflectance measurements combined with digital image processing of color intensity (RGB coordinates), qualitative and quantitative analyte detection was assessed after the colorimetric reaction took place inside the sensing membrane. A suitable linear relationship was found between the sensor response and analyte concentration, and the results were validated by a thymol-PDMS-based sensor based on the Berthelot reaction. The suggested sensing device offers advantages such as rapidity, versatility, portability, and employment of non-toxic reagents that facilitate in situ analysis in an energy-efficient manner.

Monofunctional pyrenes at carbon nanotube electrodes for direct electron transfer H2O2 reduction with HRP and HRP-bacterial nanocellulose.

The non-covalent modification of carbon nanotube electrodes with pyrene derivatives is a versatile approach to enhance the electrical wiring of enzymes for biosensors and biofuel cells. We report here a comparative study of five pyrene derivatives adsorbed at multi-walled carbon nanotube electrodes to shed light on their ability to promote direct electron transfer with horseradish peroxidase (HRP) for H2O2 reduction. In all cases, pyrene-modified electrodes enhanced catalytic reduction compared to the unmodified electrodes. The pyrene N-hydroxysuccinimide (NHS) ester derivative provided access to the highest catalytic current of 1.4 mA cm-2 at 6 mmol L-1 H2O2, high onset potential of 0.61 V vs. Ag/AgCl, insensitivity to parasitic H2O2 oxidation, and a large linear dynamic range that benefits from insensitivity to HRP "suicide inactivation" at 4-6 mmol L-1 H2O2. Pyrene-aliphatic carboxylic acid groups offer better sensor sensitivity and higher catalytic currents at ≤ 1 mmol L-1 H2O2 concentrations. The butyric acid and NHS ester derivatives gave high analytical sensitivities of 5.63 A M-1 cm-2 and 2.96 A M-1 cm-2, respectively, over a wide range (0.25-4 mmol-1) compared to existing carbon-based HRP biosensor electrodes. A bacterial nanocellulose pyrene-NHS HRP bioelectrode was subsequently elaborated via "one-pot" and "layer-by-layer" strategies. The optimised bioelectrode exhibited slightly weaker voltage output, further enhanced catalytic currents, and a major enhancement in 1-week stability with 67% activity remaining compared to 39% at the equivalent electrode without nanocellulose, thus offering excellent prospects for biosensing and biofuel cell applications.

Study of the Stability of Citrate Capped AgNPs in Several Environmental Water Matrices by Asymmetrical Flow Field Flow Fractionation.

Asymmetrical flow field-flow fractionation (AF4) coupled to UV-Vis and dynamic light scattering (DLS) detectors in series, was tested for stability studies of dispersions of citrate-capped silver nanoparticles (AgNPs) in several water matrices. The main goal is to provide knowledge to understand their possible behavior in the environment for short times since mixturing (up to 180 min). Ultrapure (UPW), bottled (BW1, BW2), tap (TW), transitional (TrW) and sea water (SW) matrices were assayed. Observations were compatible with the aggregation of AgNPs, a change in the plasmon band and a size growth with time were done. Fractograms showed different evolution fingerprints in the function of the waters and batches. The aggregation rate order was BW2, SW, TrW, BW1 and TW, being BW2 the lowest and TW the highest. NP aggregation can be induced by increasing the salt concentration of the medium, however transitional and sea waters did not follow the rule. Both matrices presented a lower aggregation rate in comparison with other aqueous matrices with much lower ionic strength (BW1 and TW), which can be explained by the potential presence of dissolved organic matter and/or the high concentration of halides providing their stabilization and passivation, respectively. AF4 provides relevant information with respect to static DLS and UV-Vis Spectroscopy showing that at least two populations of aggregates with different sizes between them, depending on both, the mixture time for a given matrix and type of water matrix for the same time.

Aqueous Dilution of Noble NPs Bulk Dispersions: Modeling Instability due to Dissolution by AF4 and Stablishing Considerations for Plasmonic Assays.

Among different nanomaterials, gold and silver nanoparticles (AuNPs and AgNPs) have become useful tools for a wide variety of applications in general, and particularly for plasmonic assays. Particle size and stability analysis are key elements for their practical applications since the NPs properties depend on these parameters. Hence, in the present work, asymmetrical flow field flow fractionation (AF4) coupled to UV-Vis and dynamic light scattering (DLS) detectors in series, has been evaluated for stability studies of citrate-capped AuNPs and AgNPs aqueous dispersions. First, experimental parameters, such as mobile phase or cross-flow rate were optimized. Sodium azide to pH 7 for AuNPs and pH 9.2 for AgNPs were selected as the optimum mobile phase. The analytical response of bulk dispersions of AuNPs (20, 40, 60 and 80 nm) and AgNPs (20, 40 and 60 nm) and their dilutions have been studied. Fractograms showed a decrease on the absorbance signal in diluted dispersions as a function of time and particle size for the diluted dispersions that can be explained by dissolution in diluted dispersion since hydrodynamic diameter was constant. The results indicated that the dependence of the signal with time was more intense for AgNPs than for AuNPs, which can be correlated with its lower stability. These findings should be considered when plasmonic assays are realized. Here, assays involving non-oxidant acidic acids as use cases, were tested for several batches of NPs and considerations about their stability and operability stablished.

Rapid evaluation of ammonium in different rain events minimizing needed volume by a cost-effective and sustainable PDMS supported solid sensor.

The presence of ammonium ion in rainwater is due to atmospheric processes which involve its scavenging from gas phase and particulate matter. The fractionated samplings of rainwater can provide information about these processes and their potential sources. However, only a low sample volume may be available, which constrained the analysis in general and more particularly in situ mode. For minimizing this limitation, this work proposes a polydimethylsiloxane (PDMS)-salicylate sensor that produces a color change. The embedding of solid reagents into PDMS was optimized. Good analytical characteristics (analysis time of 10 min, sample volume of 500 µL, limit of detection 0.03 µgmL-1) were obtained. Furthermore, other features of the method such as carbon footprint, equipment cost, residues, toxicity and safety have to be taken into account to be assessed according to the Green Analytical Chemistry approach. In this sense, the hexagon tool was employed for comparing the proposed sensor with methods based on the same reaction as well as with general methods for the ammonium analysis in water (using luminol, ion selective electrode, Nessler and modified Roth method). The proposed method based on PDMS-salicylate sensor stands out from all the others by its sustainability, particularly, in terms of low carbon footprint, residues and cost. The method was applied to fractionated samplings in a suburban site (Galicia, Northwestern Spain) and a higher contribution of the rainout process was observed. When long-duration rain events were analyzed, a relationship between the sampling time and ammonium concentration could indicate a loss of ammonium ion over time. The research focuses on developing an innovative PDMS-sensor, for monitoring ammonium determination in rainwater under wide conditions (scavenging process).

Innovations in Extractive Phases for In-Tube Solid-Phase Microextraction Coupled to Miniaturized Liquid Chromatography: A Critical Review.

Over the past years, a great effort has been devoted to the development of new sorbents that can be used to pack or to coat extractive capillaries for in-tube solid-phase microextraction (IT-SPME). Many of those efforts have been focused on the preparation of capillaries for miniaturized liquid chromatography (LC) due to the reduced availability of capillary columns with appropriate dimensions for this kind of system. Moreover, many of the extractive capillaries that have been used for IT-SPME so far are segments of open columns from the gas chromatography (GC) field, but the phase nature and dimensions are very limited. In particular, polar compounds barely interact with stationary GC phases. Capillary GC columns may also be unsuitable when highly selective extractions are needed. In this work, we provide an overview of the extractive capillaries that have been specifically developed for capillary LC (capLC) and nano LC (nanoLC) to enhance the overall performance of the IT-SPME, the chromatographic separation, and the detection. Different monolithic polymers, such as silica C18 and C8 polymers, molecularly imprinted polymers (MIPs), polymers functionalized with antibodies, and polymers reinforced with different types of carbon nanotubes, metal, and metal oxide nanoparticles (including magnetic nanoparticles), and restricted access materials (RAMs) will be presented and critically discussed.