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.

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.

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.

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.

Scaling the Analytical Information Given by Several Types of Colorimetric and Spectroscopic Instruments Including Smartphones: Rules for Their Use and Establishing Figures of Merit of Solid Chemosensors.

The analytical information given by different types of instruments was scaled in order to establish suitably the figures of merit of a given methodology based on color measurements. Different lab and portable instruments, including smartphones with and without a miniaturized spectrophotometer accessory, have been tested. In order to obtain broad information and using objective criteria, these instruments have been compared from (1) the analytical point of view, considering mainly the detection limit (limits of detection [LODs]), selectivity, accuracy and intra- and interday precision, size, components, and costs; and (2) the environmental point of view, based on their footprint as kilograms of CO2. No significant differences in the precision were obtained with RSD (%) values lower than 10% for all of the instruments, but the achieved values of LOD, selectivity, accuracy, and cost were different. Footprints of CO2 were better for portable instrumentation, especially for smartphones. Three solid chemosensors made of different materials (PDMS, paper, or nylon) have been tested for the determination of ammonia and hydrogen sulfide at different concentration levels (ppb levels). As a result of this study, some rules for selecting the instrument for obtaining the required information have been established. Two apps have been developed for quantitation by smartphones, one for working with RGB values and the other for spectra obtained by the miniaturized spectrophotometer coupled to a smartphone.

Portable solid sensor supported in nylon for silver ion determination: testing its liberation as biocide.

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.

New Reusable Solid Biosensor with Covalent Immobilization of the Horseradish Peroxidase Enzyme: In Situ Liberation Studies of Hydrogen Peroxide by Portable Chemiluminescent Determination.

Herein, we reported a chemiluminescent biosensor based on the covalent immobilization of the horseradish peroxidase (HRP) enzyme on a polydimethylsiloxane (PDMS) support to quantify in situ hydrogen peroxide (H2O2). The chemiluminescent reaction based on the use of luminol as an oxidizable substrate, with HRP as the catalyst, has been used in order to quantify H2O2 as the oxidizing agent. The performance of the proposed biosensor has been demonstrated to determine H2O2 liberated by cells in a culture medium and for evaluating the delivery of H2O2 from denture cleaner tablets, as examples of application. For both analyses, the results indicated that the biosensor is cost-effective, sensitive, and selective with a detection limit of 0.02 µM and good linearity over the range 0.06-10 µM. Precision was also satisfactory (relative standard deviation, % RSD < 6). The strength of this biosensing system is the simplicity, portability, and reusability of the devices; it can be applied up to 60 times with 90% of its activity maintained.

Nylon-Supported Plasmonic Assay Based on the Aggregation of Silver Nanoparticles: In Situ Determination of Hydrogen Sulfide-like Compounds in Breath Samples as a Proof of Concept.

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 (<10%) and selectivity were obtained. The new sensor reported was stable, sensitive, inexpensive, disposable, safe, and user-friendly. Furthermore, it has successfully been applied to determine VSCs expressed as hydrogen sulfide in breath samples (2 L and 250 mL) as a proof of concept. The limit of detection can be improved by increasing the exposition time, if necessary.

Quantifying both ammonium and proline in wines and beer by using a PDMS composite for sensoring.

Two of the reagents involved in the Berthelot's reaction, thymol and nitroprusside, were embedded in a PDMS composite in order to apply this assay to determine ammonium and proline, in wine and beers. Safety, portability, rapidity, cost-effectiveness and simplicity of the assay were improved. For the proline determination, a modified Berthelot's reaction, which included a ring cleavage of proline, was optimized. The accuracy of the assay was tested. The limits of detection for ammonium was 0.12 µg mL-1 and for proline was in the range from 0.7 to 4.1 µg mL-1, depending on the kind of wine (white, red, or sweet), for beer the LOD was 6 µg mL-1. The precision achieved was slower than 10%. The accuracy of the assay was tested by means of a confirmatory validation study. Good results were obtained for real samples.

Delivering Inorganic and Organic Reagents and Enzymes from Zein and Developing Optical Sensors.

Nowadays, interest in using environmentally friendly materials is increasing in many fields. However, the rational design of sensors with biodegradable materials is a challenge. The main aim of this work is to show the possibility of using zein, a protein from corn, as a biodegradable and low-cost material for immobilizing, stabilizing, and delivering different kind of reagents for developing optical sensors. Enzymes, metallic salts, and aromatic and small organic compounds were tested. In addition, different techniques of immobilization, entrapment and adsorption, were used, and different formats, such as solid devices and also multiwell platforms, were proposed. The capacity of zein for immobilizing two reagents together, enzyme and substrate, into a multianalysis format was also shown. Two applications were developed as examples: a colorimetric assay based on a ferric hydroxamate reaction for ester drugs, which was applied in atropine determination in pills, and a fluorimetric enzymatic multiwell-plate biodevice applied in phosphate determination in human serum and urine. Zein demonstrated being not only a green alternative but also a versatile polymer for developing sensors from reagents with different natures in different formats and matrices, thereby resulting in different applications.

New Tools for Characterizing Metallic Nanoparticles: AgNPs, A Case Study.

Currently, transmission electron microscopy (TEM) is the main technique for estimating the sizes of spherical nanoparticles (NPs) and through them, their concentrations. This paper demonstrates for the first time that C18 reversed-phase capillary liquid chromatography (Cap-LC) coupled to diode array detection (DAD) has the potential to estimate mean concentrations of silver nanoparticles (AgNPs) and thereby determine their average size. Direct injection of the sample without previous extraction or separation steps is carried out. Only a unique standard with a known AgNP size is needed for the calibration. In a first approach, the new method has been tested over silver nanoparticles, produced using different methods of synthesis, and their water dilutions. Good results were achieved: relative errors ranged up to 5% compared with TEM. Also stability and functionality-related NP properties, as well as nonspherical AgNPs, can be studied using this method. Moreover, by coupling online in-tube solid-phase microextraction (IT-SPME) to Cap-LC-DAD, the effect of the dilution can be studied as particles distribute by polarity in two groups, a distribution that responds to average particle size of not only AgNPs, but also gold nanoparticles (AuNPs). In such a distribution, the average particle size is correlated with the peak area ratio. Additionally, besides higher sensitivity and concentration-dependent signals, IT-SPME-Cap-LC responds to changes in the particle's hydrodynamic diameter allowing, for instance, the detection of cationic surfactants. Size-exclusion and hydrophobic effects are the mechanisms involved to explain this behavior.

Microextraction with phases containing nanoparticles.

In this article, the state of the art of microextraction techniques that involve nanoparticles or nanomaterials (NPs) is reviewed, with special emphasis on the applications described in the biomedical field. The uses and advantages of the different types of NPs such as carbon nanotubes (either single- and multi-walled) and other carbon-based materials, metallic NPs, including gold, silver and magnetic NPs, and silica NPs are summarized. The main strategies used to modify the selectivity, extractive capacity and/or the stability of NPs through a chemical reaction are also reviewed. The potential advantages of NPs in different forms of off-line and on-line microextraction are discussed, and illustrative examples of application in the biomedical field are shown.