This work demonstrates the fabrication of UV-responsive devices made of common packaging materials and photocatalytically active hydrogels. Using bubble wraps, a common packaging material as enclosures of a UVsensitive photocatalytic probe, a readily deployable device was created for visualizing exposure-dependent color changes induced by varying doses of UV exposure. The signal occurred from the photocatalytic decomposition of a colored dye (methyl orange) by TiO2, entrapped in agarose hydrogel that is stored within the pouches of bubble cushion wrap. Sensitivity to UV radiation dose could be tuned by varying the amount of catalyst (from 8.3 to 50 mg L1) and the concentration of indicator dye (from 0.02 to 0.04 % w/v) or by using photoprotective coatings composed of PVA membranes enriched with a hydrophilic sunscreen agent (1.25-3.75 mg sunscreen per g of PVA). The probe was sensitive to a wide range of UV radiation spanning from UVC (254 nm) to UVA (365 nm), enabling its application to a variety of applications involving UV exposure. As a demonstration, the devices were used to monitor sunlight exposure under variable conditions involving direct solar exposure, intermittent exposure, and in aquatic environments. The reactivity of the probe could be tuned from 1.8 x 106 J m(-2), which is adequate to qualitatively indicate the UV radiation doses for the synthesis of vitamin D and the induction of erythema to fair skin types, to 7.2 x 106 J m(-2) with a PVA membrane enriched with a sunscreen agent. Such high doses can be used to alert potential sunburn for darker and brown skin types from prolonged exposure to UV light and sunlight.

This work demonstrates that the packaging material commonly called "bubble wraps" (Aeroplast) can be leveraged to serve as a probe to visible sunlight exposure. This probe relies on a newly developed layered metal selenide photocatalyst with the general formula (DMAH)(2x)MnxSn3-xSe6 (DMSe-1) (x = 1.3-1.7; DMAH(+) = dimethylammonium), featuring a narrow bandgap of 0.76 eV, in addition to an indicator dye and a reducing agent. The photochemically sensitive probe is introduced into the air-filled compartments of bubble wraps and undergoes photocatalytic degradation, resulting in a chromatic response to sunlight exposure. The probe's sensitivity to variable irradiation doses can be adjusted by varying the amount of the photocatalyst. The color intensity correlates with the absorbed irradiation dose, allowing for qualitative assessment by the naked eye or quantitative measurement using the RGB color system. The results obtained from the new probe agree with those obtained from standard sunlight pyranometers (r = 0.98), with an average error of <15%. This suggests that beyond their use as protective coatings, bubble wraps can be successfully repurposed as visible light sensors. Furthermore, this study describes the initial use of metal chalcogenides as visible light probes, potentially paving the way for the development of innovative light-sensitive materials.

In this work, the total content of seven metallic elements (Fe, Cu, Zn, Mg, Pb, Ni, and Co) in common edible herbs was determined and related to their bioaccessibility by an in vitro human digestion model. Specifically, the unified bioaccessibility protocol developed by the BioAccessibility Research Group of Europe (BARGE) was used to determine the release of each element during gastric and gastrointestinal digestion. The results show that Fe, Zn, and Mg are released during gastric digestion (34–57% Fe, 28–80% Zn, 79–95% Mg), but their overall bioaccessibility is reduced in the gastrointestinal tract (<30%). On the contrary, Cu is more bioaccessible during gastrointestinal digestion (38–60%). Pb, Ni, and Co exhibited similar bioaccessibility in both gastric and gastrointestinal fluids. Principle component analysis of the data shows that the classification of the nutritional value of herbs differs between the total and the gastrointestinal concentration, suggesting that the total concentration alone is not an adequate indicator for drawing secure conclusions concerning the nutritional benefits of edible plant species.

The cornerstone of nanomaterial-based sensing systems is the synthesis of nanoparticles with appropriate surface functionalization that ensures their stability and determines their reactivity with organic or inorganic analytes. To accomplish these requirements, various compounds are used as additives or growth factors to regulate the properties of the synthesized nanoparticles and their reactivity with the target analytes. A different rationale is to use the target analytes as additives or growth agents to control the formation and properties of nanoparticles. The main difference is that the analyte recognition event occurs before or during the formation of nanoparticles and it is based on the reactivity of the analytes with the precursor materials of the nanoparticles (e.g., metal ions, reducing agents, and coatings). The transition from the ionic (or molecular) state of the precursor materials to ordered nanostructured assemblies is used for sensing and signal transduction for the qualitative detection and the quantitative determination of the target analytes, respectively. This review focuses on assays that are based on analyte-mediated regulation of nanoparticles' formation and differentiate them from standard nanoparticle-based assays which rely on pre-synthesized nanoparticles. Firstly, the principles of analyte-mediated nanomaterial sensors are described and then they are discussed with emphasis on the sensing strategies, the signal transduction mechanisms, and their applications. Finally, the main advantages, as well as the limitations of this approach, are discussed and compared with assays that rely on pre-synthesized nanoparticles in order to highlight the major advances accomplished with this type of nano-sensors and elucidate challenges and opportunities for further evolving new nano-sensing strategies.

This work reports a chemiluminescence assay for the highly selective determination of cysteine in biological fluids without separation techniques. The method is based on the ability of cysteine to selectively enhance the metal-catalyzed chemiluminescence generated by the oxidation of luminol from gold tetrachloride anions under alkaline conditions. The selectivity of the method stems from the fact that, under strongly alkaline conditions, the formation of the four-membered ring transition state of cysteine is less favorable as compared to the formation of the respective 5- and 9- membered ring transition states of homocysteine and glutathione, respectively. These transition states exert stronger hindrance and hydrophobic interactions repelling the negatively charged luminol dianion and possibly exhibit lower reducing ability for dissolved oxygen, towards the formation of superoxide radicals, thus reducing the oxidation of luminol. Under the optimum experimental conditions, the linear range of the method extended from 0.5 to 20 μΜ while cysteine could be determined at concentrations as low as 0.5 μM, with good reproducibility (<3.5%) and recoveries between 80 and 93% in artificial and real biological fluids.

This work describes a novel and easy to use method for the determination of biologically important thiols that relies on their ability to inhibit the catalytic enlargement of AuNP seeds in the presence of ACl(4) ions and trigger their aggregation. UV-vis spectroscopic monitoring of the plasmon resonance bands of the formed AuNPs showed that the spectral and color transitions depend both on the concentration and the structure of biothiols. The colorimetric changes induced by biothiols were quantified in the concentration range from 5 to 300 mu M in the RGB color system with digital photometry using a commercially available flatbed scanner as detector. On the basis of these results, the applicability of the method was tested to the determination of glutathione in red blood cells and cysteine in blood plasma with satisfactory recoveries (88.7-96.5%), low detection limits (1.0 mu M), good selectivity against major biomolecules under physiologically relevant conditions and satisfactory reproducibility (<8%). The method requires minimum technical expertise, is easy to use and is performed without scientific equipment, holding promise as a simple assay of biothiol testing even by non-experts. (C) 2020 Elsevier B.V. All rights reserved.

This work describes a new, low-cost and simple-to-use method for the determination of free biothiols in biological fluids. The developed method utilizes the interaction of biothiols with gold ions, previously anchored on micellar assemblies through electrostatic interactions with the hydrophilic headgroup of cationic surfactant micelles. Specifically, the reaction of AuCl4− with the cationic surfactant cetyltrimethyl ammonium bromide (CTAB) produces an intense orange coloration, due to the ligand substitution reaction of the Br− for Cl− anions, followed by the coordination of the AuBr4− anions on the micelle surface through electrostatic interactions. When biothiols are added to the solution, they complex with the gold ions and disrupt the AuBr4−–CTAB complex, quenching the initial coloration and inducing a decrease in the light absorbance of the solution. Biothiols are assessed by monitoring their color quenching in an RGB color model, using a flatbed scanner operating in transmittance mode as an inexpensive microtiter plate photometer. The method was applied to determine the biothiol content in urine and blood plasma samples, with satisfactory recoveries (i.e., >67.3–123% using external calibration and 103.8–115% using standard addition calibration) and good reproducibility (RSD < 8.4%, n = 3).

A new method for the determination of chloride anions in sweat is described. The novelty of the method relies on the different photochemical response of silver ions and silver chloride crystals when exposed to UV light. Silver ions undergo an intense colorimetric transition from colorless to dark grey-brown due to the formation of nanosized Ag while AgCl exhibits a less intense color change from white to slightly grey. The analytical signal is obtained as mean grey value of color intensity on the paper surface and is expressed as the absolute difference between the signal of the blank (i.e., in absence of chloride) and the sample (i.e., in the presence of chloride). The method is simple to perform (addition of sample, incubation in the absence of light, irradiation, and offline measurement in a flatbed scanner), does not require any special signal processing steps (the color intensity is directly measured from a constant window on the paper surface without any imager processing) and is performed with minimum sample volume (2 μL). The method operates within a large chloride concentration range (10–140 mM) with good detection limits (2.7 mM chloride), satisfactory recoveries (95.2–108.7%), and reproducibility (<9%). Based on these data the method could serve as a potential tool for the diagnosis of cystic fibrosis through the determination of chloride in human sweat.

Photography-based photometry is a technique developed to perform high throughput UV photometric analysis without instrumental detectors in resource-limited settings. Its principle relies on the illumination of a sample with UV irradiation and then capturing the transmitted irradiation on a photosensitive paper surface. Therefore, the photosensitive surface acts as a detector for the determination of the concentration of analytes in the sample. This work aims to investigate the optimum photosensitive paper coatings for capturing the transmitted UV irradiation. To this end, photosensitive coatings based on silver, iron, and dichromate salts were tested using three assays of pharmaceutical and biochemical interest. The results from both calibrations, using standard solutions and the application in real samples, show that photosensitive coatings based on iron salts provide the best results. Importantly, the detection limits and the linear range of the calibration curves were better than those obtained with standard photometry. Based on these findings, cyanotype green papers, are proposed as optimum detectors for photography-based photometry. This finding simplifies the operation of the technique enabling the fabrication of prototype readers for analytical assays performed in resource limited settings, point-of-need applications or in the field.

This study describes the development of a sequential extraction procedure for the evaluation of metal nanoparticle mobility and bioaccessibility in soils. The procedure, that was developed using gold nanoparticles (AuNPs) as model species, relies on the fractionation of nanoparticles by sequentially dissolving soil matrix components (carbonates, metal oxides, organic matter and mineral phases) in order to release the entrapped nanoparticle species in the extract solution. By summing up the concentration of AuNPs recovered in each fraction it was found that 93.5% of the spiked AuNP concentration could be recovered which satisfactorily represents the nominal AuNP concentration in the soil. The efficiency of the procedure was found to depend on several procedural artifacts related to the separation of AuNPs from soil colloids and the reactivity of the extraction reagents with AuNPs and their precursor metal ions. Based on the results obtained a protocol for the speciation of the AuNPs and Au ions in the soil sample was also developed. The results of the study show that both AuNPs and Au ions are mainly associated with soil organic matter, which significantly reduces their mobility, while a small amount (<10%) is associated with metal oxides which are more mobile and potentially bioaccessible. The developed procedure provides a springboard for further development of sequential extraction procedures of metal nanoparticles in soils that could be used to assess both the exposure and release of metal nanoparticles and their precursor metal ions in the environment (as total extractable concentration) as well as provide evidence regarding their bioaccessibility and potential bioavailability by determining the concentration of nanoparticles in each specific soil fraction. (C) 2020 Elsevier Ltd. All rights reserved.

The determination of biological aminothiols (mainly cysteine, homocysteine, and glutathione) is an important tool in the clinical diagnosis of many disorders and diseases. Therefore, the development of new chemical sensors and probes has attracted considerable attention. Nanomaterials have a profound role in this endeavor since they offer some unique advantages such as lower cost, faster analysis times, and ease of operation compared to classic instrumental techniques such as liquid chromatography and capillary electrophoresis. In this review, we provide a focused outline on the most recent evolvements in optical biothiol sensing using nanomaterials. The most important reaction mechanisms and detection strategies are summarized and compared in terms of their sensitivity and selectivity against various biothiol species. Critical fields for future research and challenges are discussed and elucidated.

This work describes a new, equipment-free, generic method for the determination of sulfur-containing compounds that is based on their ability to slow down the photoreduction kinetics of gold ions to gold nanoparticles. The method involves tracking the time required for a red coloration to appear in the tested sample, indicative of the formation of gold nanoparticles, and compare the measured time relative to a control sample in the absence of the target analyte. The method is applicable with minimal and simple steps requiring only two solutions (i.e., a buffer and a gold solution), a source of light (UV or visible), and a timer. The method responds to a large variety of sulfur-containing compounds including thiols, thioesters, disulfides, thiophosphates, metal-sulfur bonds, and inorganic sulfur and was therefore applied to the determination of a variety of compounds such as dithiocarbamate and organophosphorous pesticides, biothiols, pharmaceutically active compounds, and sulfides in different samples such as natural waters and wastewater, biological fluids, and prescription drugs. The analytical figures of merit of the method include satisfactory sensitivity (quantitation limits at the low μM levels), good recoveries (from 93 to 109%), and satisfactory reproducibility (from 4.8 to 9.8%). The method is easily adoptable to both laboratory settings and nonlaboratory conditions for quantitative and semiquantitative analysis, respectively, is user-friendly even for the minimally trained user, and can be performed with limited resources at low cost.

This work describes the development of a new green solid-phase extraction approach, which is based on the use of low-cost extraction discs composed of plain filter papers that are covered with a synthetic wax-like coating. The filter papers are printed in a commercial solid ink printer, which dispenses a synthetic wax-like ink on the surface of the paper, to cover the hydrophilic cellulose fibre matrix with an interface of lipophilic domains where non-polar analytes can partition through hydrophobic interactions. The modified paper filters were used to extract hydrophobic organic compounds from water samples following the customary procedure of solid-phase extraction without sorbent preconditioning and needless of high-vacuum sources. As a proof-of-concept application, a series of non-polar organic UV filters were used as model analytes to optimise the extraction parameters and evaluate the performance of the method in spiked water samples. Based on this principle, a new sample preparation platform with low environmental footprint has been developed that enables extraction to be carried out using low-cost, environmental benign and non-toxic conventional materials. The advantages and disadvantages of the method, alongside with its future prospects towards the development of custom-made printed extraction kits', are envisioned and discussed.

This work presents a new method for the sensitive and selective determination of gold nanoparticles in water samples. The method combines a sample preparation and enrichment step based on cloud point extraction with a new detection motif that relies on the optical incoherent light scattering of a nano-hybrid assembly that is formed by hydrogen bond interactions between gold nanoparticles and dithiotreitol-functionalized CdS quantum dots. The experimental parameters affecting the extraction and detection of gold nanoparticles were optimized and evaluated to the analysis of gold nanoparticles of variable size and surface coating. The selectivity of the method against gold ions and other nanoparticle species was also evaluated under different conditions reminiscent to those usually found in natural water samples. The developed method was applied to the analysis of gold nanoparticles in natural waters and wastewater with satisfactory results in terms of sensitivity (detection limit at the low pmol L-1 levels), recoveries (>80%) and reproducibility (<9%). Compared to other methods employing molecular spectrometry for metal nanoparticle analysis, the developed method offers improved sensitivity and it is easy-to-operate thus providing an additional tool for the monitoring and the assessment of nanoparticles toxicity and hazards in the environment. (C) 2016 Elsevier B.V. All rights reserved.

This work describes a new method for the extraction and determination of gold nanoparticles in environmental samples by means of in-situ suspended aggregate microextraction and electrothermal atomic absorption spectrometry. The method relies on the in-situ formation of a supramolecular aggregate phase through ion-association between a cationic surfactant and a benzene sulfonic acid derivative. Gold nanoparticles are physically entrapped into the aggregate phase which is separated from the bulk aqueous solution by vacuum filtration on the surface of a cellulose filter in the form of a thin film. The film is removed from the filter surface and is dissociated into an acidified methanolic solution which is used for analysis. Under the optimized experimental conditions, gold nanoparticles can be efficiently extracted from water samples with recovery rates between 81.0–93.3%, precision 5.4–12.0% and detection limits as low as 75femtomolL−1 using only 20mL of sample volume. The satisfactory analytical features of the method along with the simplicity indicate the efficiency of this new approach to adequately collect and extract gold nanoparticle species from water samples.

Estrogen and estrogen receptors (ERs) have been reported to play protective roles in ischemia/reperfusion (I/R)-mediated injury, but the detailed mechanism remains to be fully understood. Nitric oxide (NO) and reactive oxygen species (ROS) also play important roles in the I/R process; however, due to the lack of sensitive and reproducible in vivo monitoring systems, we still do not have direct evidence for the effect of NO and ROS in vivo. In this study, we have established reliable in vivo monitoring systems to measure the variations in circulating ROS and NO during the I/R. We found that during the first few minutes of post-ischemia reperfusion, an oxidative burst occurred concurrent with a rapid loss of NO. Expression of ERβ in the endothelium reduced these effects that accompanied an attenuation in myocardial infarction and vascular damage. Further investigation showed that Tie2-driven lentivirus delivery of ERβ to the vascular wall in rats increased the expression of its target genes in the endothelium, including ERRα, SOD2 and eNOS. These changes modulate ROS generation, DNA damage, and mitochondrial function in rat endothelial cells. We also found that ERβ expression in the endothelium reduced ROS generation and restored mitochondrial function in cardiomyocytes; this may be due to ERβ-mediated NO formation and its high diffusibility to cardiomyocytes. We conclude that ERβ expression in the endothelium ameliorates ischemia/reperfusion-mediated oxidative burst and vascular injury.

The development of fluorescent turn-on probes for the determination of inorganic anions based on fluorescent semiconductor nanocrystals (quantum dots) has recently attracted great attention. Methods reported so far enable anion sensing at elevated concentration levels and usually with low selectivity against other abundant matrix components. In this work, we describe an alternative approach that combines the appropriate modulation of nanocrystal surface chemistry (i.e., stabilization) with rational design and modulation of the experimental conditions (i.e., flow injection analysis) in order to deliver an expedient flow through method that enables the determination of phosphate at low concentration levels and with good selectivity. The developed method was successfully applied to the determination of phosphate in artificial and human saliva with good analytical features in terms of reproducibility and repeatability (2.3-9.2%), recoveries from fortified samples (96.0-112.0%), linearity of response curves to phosphate concentrations (R-2>0.99), and satisfactory sensitivity (<1 mu M), providing a significant improvement to previous fluorescent turn-on quantum dot probes.

With the increasing interest in the health benefits arising from the consumption of dietary products rich in antioxidants, there exists a clear demand for easy-to-use and cost-effective tests that can be used for the identification of the antioxidant power of food products. Paper-based analytical devices constitute a remarkable platform for such expedient and low-cost assays with minimal external resources but efforts in this direction are still scarce. In this work we introduce a new paper-based device in the form of a sensor patch that enables the determination of antioxidant activity through analyte-driven on-paper formation of gold nanoparticles. The principle of detection capitalizes, for the first time, on the on-paper nucleation of gold ions to its respective nanoparticles, upon reduction by antioxidant compounds present in an aqueous sample. The ensuing chromatic transitions, induced on the paper surface, are used as an optical "signature" of the antioxidant strength of the solution. The response of the paper-based sensor was evaluated against a large variety of antioxidant species and the respective dose response curves were constructed. On the basis of these data, the contribution of each species according to its chemical structure was elucidated. For the analysis of real samples, a concentration-dependent colorimetric response was established against Gallic acid equivalents over a linear range of 10 mu M-1.0 mM, with detection limits at the low and ultra-low mM levels (i.e. < 1.0 mu M) and satisfactory precision (RSD = 3.6-12.6%). The sensor has been tested for the assessment of antioxidant activity in real samples (teas and wines) and the results correlated well with commonly used antioxidant detection methods. Importantly, the sensor performed favorably for long periods of time when stored at moisture-free and low temperature conditions without losing its activity thus posing as an attractive alternative to the assessment of antioxidant activity without specialized equipment. The use of the sensor by non-experts for a rapid assessment of natural products in field testing is envisioned. Importantly, we demonstrate for the first time that analyte-mediated growth of nanomaterials directly on the paper surface could open new opportunities in paper-based analytical devices. (C) 2014 Elsevier B. V. All rights reserved.

Objective Free fatty acids from tobacco smoke may be important toxic elements since they can form a lipophilic complex with ferrous iron and then transport the iron into mammalian cells. Although such iron loading was earlier found to increase the oxidative susceptibility of cell membrane polyunsaturated fatty acids, additional toxic effects of fatty acid:iron complexes are little known. Methods Using simple eukaryotic cells of Saccharomyces cerevisiae, the synergistic effets of fatty acid:iron on yeast cytotoxicity and mutagenesis were investigated. The fatty acids-mediated iron depsition in the mitocchondria and lipid oxidation, and the subsequent reactive oxygen species generation were also studied. Results The combination of iron and free fatty acids was markedly toxic, although neither single constituent had a detectable effect on yeast viability and mutagenesis. This toxicity was prevented when yeast suspensions were incubated with nitrogen, suggesting that reactive oxygen generated by mitochondrial metabolism may be involved. Indeed, respiration defective(ρ 0) yeast were relatively protected against iron:fatty acid-induced toxicity. Yeasts endowed with enhanced iron storage capability through overexpression of CCC1 were similarly protected. The cytotoxic effects of iron + fatty acids were most likely mediated by oxidant damage to membrane polyunsaturated fatty acids inasmuch as supplementation of yeast cultures with α-tocopherol or a 'lazaroid' compound(inhibitors of peroxidation of polyunsaturated fatty acids) also protected against killing. Conclusion The toxic effects of iron overload caused by iron:fatty acid complexes may be implicated in the mitochondrial metabolism. Furthermore, if these observations in yeast are pertinent to the progressive pulmonary damage associated with cigarette smoking, they imply that the seemingly innocuous fatty acids existed in tobacco smoke mayrepresent important toxic elements in the presence of trace amounts of ‘loose' iron.