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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. Graphical abstract

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 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.

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.

We propose a portable sensor, obtained by embedding luminol into the tetraethylorthosilicate/trietoxymethylsilane (TEOS/MTEOS) composite, for the quantitative determination of organic amino nitrogen and ammonium in water with the goal of achieving low levels of concentration. The method is based on the reaction between amino nitrogen compounds and hypochlorite to produce chloramino derivatives. Then, the remaining hypochlorite reacts with luminol sensor by producing a luminescence signal, which was measured by using a portable luminometer, being inversely proportional to nitrogen concentration. The liberation of the luminol from sensor is higher than 90% and the sensor is stable for at least a week at room temperature. This portable method was successfully validated and applied to the analysis of several real waters: fountain, river transition, lagoon, and seawater with recovery values between 92% and 112%, which indicated that the matrix effect was absent. The achieved limit of detection was around 10 µg·L−1, expressed as N. This sensor allows in situ monitoring owing to its simplicity, rapidity, and portability.

This paper shows a particular example to move to a sustainable circular economical process from valorization of rice straw ashes by developing a green synthesis for obtaining a useful sub-product. This strategy can palliate negative effects of the agriculture waste practices on the environment and also the obtained silica reduced nitrate content in waters. It is demonstrated that the silica synthesis developed at lab was scalable more than a hundred times with good results. Adsorption studies of nitrate in standards and real well waters at lab scale and scaling-up provided similar results. Adsorption values near to 15 mg/g for nitrate standards and 8.5 mg/g for well water were obtained until achieving the initial nitrate concentration. Experimental breakthrough curves fitted to Thomas model, which gave similar results for adsorption capacities. The adsorption capacity was checked with that obtained by a commercial resin, providing improved results. The method at large scale was compared with industrial traditional methods and green adsorbents.

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 &lt, 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.

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.

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.

A quantitative evaluation tool is proposed, which aims to assess optimal selection or/and testing of analytical methods. Objective criteria related to analytical performance, sustainability, environmental impact and economic cost are evaluated through the definition of penalty points divided into five different blocks, namely, figures of merit, toxicity and safety, residues, carbon footprint and economic cost. For each block, the overall qualification is scaled from 0 to 4 and it is depicted on a regular hexagonal pictogram that allows a user friendly comparison of analytical procedures. The present evaluation tool aims to be a guideline for evaluating and/or selecting analytical procedures that are in line with Green Chemistry philosophy, but also balancing the figures of merit needed for solving a given problem, safety and cost-effectiveness. Real examples have been tested.

A procedure for supporting silver nanoparticles (AgNPs) on nylon is proposed. Besides, the membrane has been developed as a solid-phase colorimetric plasmonic sensor for volatile sulfide compounds (VSCs) like H2S, CH3SH, and (CH3)2S. AgNP behavior in the membrane has been studied by UV-vis diffuse reflectance spectrometry, Raman spectrometry, High-resolution transmission electron microscopy (HR-TEM), and Scanning electron microscopy (SEM). The sensor responded by changing its color from yellow in absence of VSCs to several orange/brown colors in the function of VSC concentration as occurs in solution; an increase in the hydrodynamic diameter, estimated by both asymmetrical flow field-flow fractionation (AF4) coupled on line to Dynamic light scattering (DLS) detector and batch DLS, is achieved when sulfide is added to the citrate-capped AgNPs. Diffuse reflectance spectrometry and processed digital images obtained with a smartphone have been used as measurements and several transformations for quantitation are proposed; a linear concentration range of hydrogen sulfide from 150 to 1000 ppbv and a detection limit (LOD) of 45 ppbv were achieved, measuring after 10 min of the sensor exposition to the hydrogen sulfide atmosphere (2 L) for humidity percentages between 50 and 96% and room temperature. Satisfactory results in terms of precision (

In the present work, the footprint of carbonyl compounds in hand scent was achieved by a miniaturized method consisting of sampling with cotton gauze, extraction and derivatization using 2,4-dinitrophenylhydrazine (DNPH) and preconcentration, separation and detection by in-tube solid-phase microextraction (IT-SPME) coupled to nano-liquid chromatography/Uv–vis diode array detection. The coupling IT-SPME-nanoLC-DAD was solved by using a two-valve system: the first valve for loading the sample and the second one to perform IT-SPME. To this aim, a nanoparticle-based capillary column was employed. Firstly, the transfer time from the load loop to the NP-based capillary column in the IT-SPME system was optimized. Additionally, the conditioning and clean-up steps were also studied. For the chromatographic separation of DNPH derivatives, gradient elution mode (acetonitrile/water) and a C18 nanocolumn were employed. The detection limits achieved were between 0.5 and 1.5 μg/L and % rsd was lower than 5% for quantification limits. The proposed methodology gave rise to different chromatographic profiles of carbonyl compounds in the hand scent of several volunteers. These profiles were obtained by estimating the relative peak area of selected carbonyls in hand scent. Nonanal, decanal and dodecanal and other low polarity carbonyl compounds (unknown hydrazones) were detected in the odor profiles.

This paper demonstrates that the reactivity of copper (II) can be modified through its entrappment in a polymeric matrix of polydimethylsiloxane (PDMS), which makes possible the reaction into the support instead of in solution. Amino-containing compounds such as amino acids, proteins and sugars, which react with Cu (II) in solution, do not react inside the polymer. As a prove of concept, a highly specific Cu (II) PDMS-based sensor for ephedrines has been developed in this work. When the sensors are put into contact with solutions of these drugs under basic conditions, a change in their color from pale green to purple is observed. This change enables the visual identification of ephedrine (Eph) in a few min, as well as its quantification using both reflectance diffuse measurements of the sensors and color intensities of their digitalized images. The sensors show suitable analytical performance for Eph-like compounds, and provide limits of detection (LODs) of 0.3-1.0 mg, and relative standard deviations (RDSs) 10%. The method has been applied to both the qualitative and quantitative analysis of different types of liquid and solid samples (intravenous injection solution of Eph, dietary supplements and illicit drug-street samples) without the need of any special sample treatment.

Sarcosine, a potential biomarker for prostate cancer, can be detected in a solid state enzyme based biosensor using sarcosine oxidase, with particle immobilised reagents. A novel fusion protein of the fluorescent protein, mCherry, sarcosine oxidase (SOx), and the polypeptide R5 (R52-mCherry-SOx-R5-6 H), was explored, which allowed self-immobilization on silica microparticles and long-term (90 days +) retention of activity, even at room temperature. In contrast, commercial wildtype SOx lost activity in a few days. A silica-R52-mCherry-SOx-R5-6H microparticle sensor for determination of sarcosine in urine, linked the SOx coproduct, H2O2, to a measurement catalysed by horseradish peroxidase (HRP) immobilised on silica, in the presence of Amplex Ultrared (AR) to generate fluorescence at 582 nm. Silica microparticles carrying all the reagents (R52-mCherry-SOx-R5-6H, HRP and AR) were used to produce a silica-microparticle biosensor which responded to sarcosine at micromolar levels. Interference by amino acids and uric acid was examined and it was found that the silica-reagent carrying system could be calibrated in urine and responded across the clinically relevant concentration range. This contrasted with similar assays using commercial SOx, where interference inhibited the sarcosine signal measurement in urine. The microparticle biosensor was tested in urine from healthy volunteers and prostate cancer patients, showing higher concentrations of sarcosine in cancer patients consistent with previous reports of elevated sarcosine levels.

A sensor for the colorimetric estimation of the alcoholic content has been developed based on the entrapment of the reagent (4-N,N-dioctylamino)-4‘-trifluoroacetylazobenzene (ETHT 4001) into polydimethylsiloxane (PDMS) modified with tretraethylorthosilicate (TEOS). When exposed to an alcoholic media, the sensor delivers ETHT 4001 so that it reacts with alcohols, resulting in a change in the solution color. The diffusion of the entrapped ETHT 4001 from the polymeric sensor to the working solution depends on the hydrophobicity of both the sensor matrix and the media, while the time of exposure determines whether the reagent reacts with methanol, or with methanol and ethanol. Thus, the sensors are a versatile tool for the estimation of the methanol content in ethanol or in ethanol/water mixtures, and for the measurement of the total alcoholic content (methanol plus ethanol) in an hydroalcoholic media. The proposed sensors are very easy to prepare, and show good precision and long-term stability. Moreover, the reagent delivery is reversible which allows its recovery once the absorbance measurements have been made simply by adding water, so the sensors can be reutilized and the generation of wastes is reduced. The potential utility of the proposed sensors has been demonstrated by measuring the alcoholic strength of commercial spirit drinks, and the methanol content in spiked hydroalcoholic samples.

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 H

Colorimetric localized surface plasmon resonance (LSPR) as analytical response is applied for a wide number of chemical sensors and biosensors. However, the dependence of different factors, such as size distribution of nanoparticles (NPs), shape, dielectric environment, inter-particle distance and matrix, among others, can provide non-reliable results by UV–vis spectrometry in complex matrices if NP assessment is not carried out, particularly at low levels of analyte concentrations. Miniaturized liquid chromatography, capillary (CapLC) and nano (NanoLC), coupled on line with in-tube solid phase microextraction (IT-SPME) is proposed for the first time for both, controlling suitability of used noble metal NP dispersions and developing plasmonic assays. Several capped noble NPs and target analytes were tested from variations in the chromatographic profiles obtained by using diode array detection. The IT-SPME step, which influenced the chromatographic fingerprint provided by noble NP dispersions, was studied by asymmetrical flow field flow fractionation (AF4) too. We monitored NP aggregation induced by interaction with several analytes like acids and spermine (SPN). Assessment of NPs was achieved in less than 10 min and it permitted to develop suitable plasmonic tests. Here, it was also demonstrated that these assays can be followed by IT-SPME-miniaturized LC-DAD and more sensitivity and selectivity than those provided by UV–Vis spectrometry were achieved. Analysing urine samples to determine SPN as a cancer biomarker as a proof of concept is presented.

Celiac disease is an immune-mediated systemic disorder elicited by gluten and related prolamines in genetically susceptible individuals. The current treatment is a strict and lifelong gluten-free diet. However, compliance with the gluten-free diet is not always adequate and many food products contain low concentrations of gluten. The determination of dietary transgressions is a challenge for patients, physicians and dietitians. Alkylresorcinols (AR) have been proposed as sensitive and specific biomarkers of gluten consumption. In this work silica-polymer composites doped with fast blue B reagent (FB) have been used to estimate alkylresorcinols in biological samples. The proposed colorimetric device was synthetized by immobilizing FB into polydimethylsiloxane-tetraethylortosilicate composite. The assay was based on the spontaneous release of FB to the solution con-taining AR (3,5-dihydroxyhydrocinnamic acid, DHCA) and the azocomplexe formation (520 nm). The response was evaluated with UV-vis spectroscopy and chromatography (in-tube SPME-Capillary LC-DAD) to isolate DHCA signal. The spectroscopic analysis can be used as a screening tool to differentiate positive and negative samples. Meanwhile, the chromatographic assay was necessary to isolate DHCA response in positive samples. LOD was 60 ng mL-1 by adding a SPE step. Precision provided adequate results (RSD < 15%). Preliminary studies in urine samples displayed successful results, showing DHCA can be used as biomarker of gluten intake. The here pro-posed methodology clearly simplifies the dietary transgression evaluation thanks to the development of a pre -screening tool before the chromatographic analysis.

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 (0.05g Thymol in 95mL of EtOH and 5mL 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.

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.

A composite membrane containing 1,2-naphthoquinone-4-sulfonic acid sodium salt (NQS) embedded in an ionic liquid (IL)- polydimethylsiloxane (PDMS)- tetraethyl orthosilicate (TEOS)- SiO2 nanoparticles (NPs) polymeric matrix is proposed. The selected IL was 1-methyl-3-octylimidazolium hexafluorophosphate (OMIM PF6). It is demonstrated that ILs chemical additives of PDMS influenced the sol-gel porosity. The sensor analytical performance for ammonia atmospheres has been tested as a function of sampling time (between 0.5 and 312 h), temperature (25 °C and 4 °C) and sampling volume (between 2L and 22 mL) by means of diffuse reflectance measurements and sensor photos, which can be registered and saved as images by a smartphone, which permit RGB measurements too. Flexible calibration was possible, adapting it to the sampling time, temperature and sampling volume needed for its application. Calibration linear slopes (mA vs ppmv) between 1.7 and 467 ppmv−1 were obtained for ammonia in function of the several studied conditions. Those slopes were between 48 and 91% higher than those achieved with sensors without ILs. The practical application of this sensing device was demonstrated for the analysis of meat packaging environments, being a potential cost-effective candidate for in situ meat freshness analysis. NQS provided selectivity in reference to other family compounds emitted from meat products, such as sulphides. After 10 days at 4 °C ammonia liberated by the assayed meat was 20 ± 4 μg/kg and 18 ± 3 μg/kg, quantified by using diffuse reflectance and %R measurements, respectively. Homogeneity of the ammonia atmosphere was tested by using two sensors placed in two different positions inside the packages.

Analytical performance and optimization of figures of merit of a portable nano liquid chromatograph (NanoLC) with UV detection at 255 nm have been established for in place analysis. Methylxanthines: caffeine, theophylline and theobromine were selected as target analytes. A fast lab method based on IT-SPME coupled on line with capillary liquid chromatograph (CapLC) with diode array detection (DAD) was employed for comparative studies. IT-SPME and solid phase extraction were coupled off-line to NanoLC for improving instrumental parameters, mainly detection capacity and selectivity. IT-SPME or SPE/portable NanoLC based methods were superior in terms of chromatographic resolution and organic solvent consumption per sample, around 200 μL vs 10 mL for IT-SPME-CapLC-DAD. Limits of detection (LODs) obtained with the SPE/portable NanoLC were 2–10 ng/mL, which can be suitable for testing the presence of the analytes in several environmental waters in the field. As predictable, the lab method provided better LODs, between 0.1 and 0.5 ng/mL. Good linearity was achieved for both methods and precision was similar for them (≤7%). Both systems were tested for the analysis of real water samples with suitable results.

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.

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).

This paper reports the fabrication and utility of a new solid sensor, which allows the quantitation of silver ions acting as catalyst at the low micromolar level. The optical sensor was prepared by incorporating both reagents, pyrogallol red (PGR) and 1,10-phenanthroline (Phen), in a nylon membrane. The effect of parameters in determining silver-catalyzed oxidation of PGR by persulfate in the presence of Phen as an activator was studied and optimized for achieving suitable sensitivity. Semiquantitative analysis can be performed by visual inspection of the color of the sensor by comparing it with standard responses and quantitative analysis can be carried out by its diffuse reflectance (DR) measurement or by a digital image-processing tool (GIMP) using a smartphone. The sensor exhibited a linear relationship toward Ag(I) concentrations ranging from 0.4 to 10 μM or 1-25 μM and limits of detection of 0.1 μM or 0.3 μM for incubation times of 50 and 30 min, respectively. The relative standard deviation achieved for several batches of sensors was around 2%. The analysis of water samples from tap and refrigerating circuits containing solid biocides, which leach silver ions, prove that this portable and sustainable sensor is successfully operational in real situations. Graphical abstract.

The funeral chambers of the ancient city of Calakmul (Mexico) and the individuals who were buried in them have brought in recent decades new knowledge about the beliefs and funeral customs of the pre-Hispanic Maya. Tombs and bodies were prepared as part of the rituals that should favor the return of ch'ulel to the Underworld, known as Xibalba by the ancient Maya. The ch'ulel is one of the two anemic entities that inhabit the individual, equivalent to our concept of the soul. Bodies preparation included coloured scented body ointments application, with a deep symbolic connotation and probably also a conservative purpose. The aim of this research was to characterize pigments and binders used by ancient Maya in body ointments remains in human bones samples from Calakmul Maya archaeological site, and the latter, the physical–chemical identification of organic components mixed with these colours for funeral use, can be considered the great challenge of this research due to the limited results that have been gathered on the subject to date. For this purpose, a multi-analytical approach based on the combination of several non-destructive and micro-destructive analytical techniques has been selected. Pigments were studied by transmitted light optical microscopy, FT-IR spectroscopy in ATR mode, diffuse reflectance UV–VIS spectrometry, and EDX microanalysis provided elemental information in order to find characteristic elements useful to identify the unknown pigments. Surface of the samples was observed with Scanning Electron Microscopy (SEM). Gas-Chromatography coupled with Mass Spectrometry (GC–MS) and Pyrolysis-Gas-Chromatography-Mass Spectrometry (Py-GC-MS) were performed in order to collect information about organic fraction used as binding media. The multi analytical approach identified red pigments as Red Earth (or ochre) and Cinnabar, while the results obtained on organic fractions lead us to suggest the presence of lipidic and gum- based compounds.