Sensitive fluorescent chemosensor for Hg(II) in aqueous solution using 4'-dimethylaminochalcone.

Mercury (Hg) is an element with high toxicity, especially to the nervous system, and fluorescent pigments are used to visualize dynamic processes in living cells. A little explored fluorescent core is chalcone. Herein, we synthesized chalcone (2E)-3-(4-(dimethylamino)phenyl)-1-phenylprop-2-en-1-one (8) and assessed its photophysical properties. Moreover, the application of this chemosensor in aqueous media shows a selective fluorescence quenching effect with Hg(II). The figures of merit for the chemosensor were calculated to be LOD = 136 nM and LOQ = 454 nM, as well as a stoichiometry of 1:1. Furthermore, the association constant (Ka) and fluorescence quenching constant (KSV) were calculated using the Benesi-Hildebrand and Stern-Volmer equations to be Ka= 9.08 × 104 and KSV= 1.60 × 105, respectively. Finally, by using a computational approach, we explain the interaction between chalcone (8) and Hg(II) and propose a potential quenching mechanism based on the blocking of photoinduced electron transfer.

Synthesis of fluorescent chalcones, photophysical properties, quantitative structure-activity relationship and their biological application.

The development of fluorescent pigments is an area of interest in several research fields due to their high sensitivity. In the current study-eight known and three new N,N-dimethylamino-chalcones (12a-k) were synthesized with good yields using the Claisen-Schmidt reaction. For each molecular system, the photophysical properties, including the maximum absorption wavelength (λAbsorption), molar absorption coefficient (ε), maximum excitation wavelength (λExcitation), maximum emission wavelength (λEmission), Stokes Shift (Δλ), fluorescence quantum yield (Φfl), fluorescence lifetime (τfl), radiative and non-radiative rate constants (kR and kNR, respectively) were evaluated. Variations in each of these properties were analyzed depending on the substituents present on each compound. To relate the chemical structures of the synthesized compounds to their photophysical properties, Hansch analysis (2D-QSPR) was applied. As a result of Hansch analysis, we found different photophysical properties related to molecular orbitals and the energy of their derivatives (Highest Occupied Molecular Orbital-HOMO, Lowest Unoccupied Molecular Orbital-LUMO, Difference between LUMO-HOMO-ΔLH, Chemical potential-µ, Hardness-η, Softness-S, and electrophilic global index-ω) as well as to the atomic charges on atoms C5, Cα, Cß, and CO. The application of this type of analysis has made it possible to understand and subsequently design new molecules with defined photophysical properties. Finally, the compounds were use as fluorescent pigment to get living cell imaging on breast cancer cells, obtaining the compound 12a as promissory alternative.

Global issues in setting legal limits on soil metal contamination: A case study of Chile.

The establishment of legal limits for soil contamination with trace elements is a global issue that has not yet been resolved. However, the resolution of any global problem begins at the national level. In this vein, we present the case of Chile, the world's leading copper producer, where soil contamination by trace elements in mining areas has been severe. We evaluated the magnitude of the ecological and human health risks from exposure to arsenic (As), copper (Cu), zinc (Zn), and lead (Pb) in soils of the La Ligua and Petorca basins, two important mining areas in Chile. Contrary to what might be expected in soils affected by Cu mining activities, As was identified as the most hazardous element in the studied soils, both in terms of ecological and human health risks. On the other hand, Chile does not currently have specific legislation establishing legal limits on soil contamination with trace elements. Since Chile is geochemically similar to New Zealand, Mexico, and Italy, we used the limits of these three countries as benchmarks. We determined the background concentrations of As, Cu, Zn, and Pb in the soils of the two river basins under study and found that they tend to exceed the limits established by foreign laws. We also found that the differences in background elemental concentrations in the studied soils were primarily due to the varied lithology of soil-forming rocks. This means that absolute "one-limit-fits-all" values of element concentrations may not be adequate to regulate the level of soil contamination in areas affected by mining. As a fundamental first step, it is necessary to establish background soil concentrations of trace elements in each river basin in Chile. It is clear that Chile urgently needs to move from rubber-stamping foreign laws to the development of national legislation on soil metal contamination.

Improving bitter pit prediction by the use of X-ray fluorescence (XRF): A new approach by multivariate classification.

Bitter pit (BP) is one of the most relevant post-harvest disorders for apple industry worldwide, which is often related to calcium (Ca) deficiency at the calyx end of the fruit. Its occurrence takes place along with an imbalance with other minerals, such as potassium (K). Although the K/Ca ratio is considered a valuable indicator of BP, a high variability in the levels of these elements occurs within the fruit, between fruits of the same plant, and between plants and orchards. Prediction systems based on the content of elements in fruit have a high variability because they are determined in samples composed of various fruits. With X-ray fluorescence (XRF) spectrometry, it is possible to characterize non-destructively the signal intensity for several mineral elements at a given position in individual fruit and thus, the complete signal of the mineral composition can be used to perform a predictive model to determine the incidence of bitter pit. Therefore, it was hypothesized that using a multivariate modeling approach, other elements beyond the K and Ca could be found that could improve the current clutter prediction capability. Two studies were carried out: on the first one an experiment was conducted to determine the K/Ca and the whole spectrum using XRF of a balanced sample of affected and non-affected 'Granny Smith' apples. On the second study apples of three cultivars ('Granny Smith', 'Brookfield' and 'Fuji'), were harvested from two commercial orchards to evaluate the use of XRF to predict BP. With data from the first study a multivariate classification system was trained (balanced database of healthy and BP fruit, consisting in 176 from each group) and then the model was applied on the second study to fruit from two orchards with a history of BP. Results show that when dimensionality reduction was performed on the XRF spectra (1.5 - 8 KeV) of 'Granny Smith' apples, comparing fruit with and without BP, along with K and Ca, four other elements (i.e., Cl, Si, P, and S) were found to be deterministic. However, the PCA revealed that the classification between samples (BP vs. non-BP fruit) was not possible by univariate analysis (individual elements or the K/Ca ratio).Therefore, a multivariate classification approach was applied, and the classification measures (sensitivity, specificity, and balanced precision) of the PLS-DA models for all cultivars evaluated ('Granny Smith', 'Fuji' and 'Brookfield') on the full training samples and with both validation procedures (Venetian and Monte Carlo), ranged from 0.76 to 0.92. The results of this work indicate that using this technology at the individual fruit level is essential to understand the factors that determine this disorder and can improve BP prediction of intact fruit.

Total mercury bias in soil analysis by CV-AFS: causes, consequences and a simple solution based on sulfhydryl cotton fiber as a clean-up step.

This study examines the matrix effect over the trueness for determining total mercury (THg) using CV-AFS. We demonstrate that matrix interferences in soils and sediment samples cannot be eliminated by acid digestion and establish the use of sulfhydryl cotton fiber (SCF), a malleable, cheap and easy to synthesize fiber, as a mandatory solution capable to overcome this bias. Using the classic CV-AFS approach, an overestimation bias for THg recovery values of >140% in a certified reference material was reported. Interference metals test was conducted, thus discarding any influence of metals in the overestimation bias. Therefore, a clean-up step using SCF was proposed, and tests with synthesized fiber did not present a dispersion of >0.08 ng L-1. Moreover, validation was performed by analyzing three certified reference material and yielding mean recovery percentages of 100% ± 1%. A validated methodology was applied to ten environmental soil samples; THg values obtained varied from 129 to 384 ng g-1. Finally, a comparison between sample results obtained and reference method did not show any significant differences (p > 0.05), thus highlighting the efficacy of SCF-CV-AFS for THg quantification in environmental solid samples.

Determination of ochratoxin A in coffee and tea samples by coupling second-order multivariate calibration and fluorescence spectroscopy.

A new method to quantify the mycotoxin ochratoxin A (OTA) in coffee and tea samples is proposed based on second-order multivariate calibration and excitation-emission fluorescence matrix (EEFM) data. Experimental conditions were optimized by studying the effect of pH and various organized media on the fluorescence signal of OTA. For each analysed matrix (coffee grains and tea leaves), several sample pretreatments and calibration methods (external or standard addition) and data processing by chemometric models (e.g., parallel factor analysis/PARAFAC and multivariate curve resolution-alternating least squares/MCR-ALS) were evaluated and discussed. The MCR-ALS algorithm provided an adequate fit to the data for both samples, while PARAFAC was satisfactory only for the tea samples. Regarding the figures of merit, the limits of detection were in the range of 0.2-0.3 ng mL-1; furthermore, low relative prediction errors, between 2% and 4%, were achieved in both the fortified and real samples. Accordingly, the proposed methodology was applied to analyse fortified roasted and green coffee and real tea leaf samples. Satisfactory recoveries were achieved (ranging from 92 to 110%), and the obtained concentrations were in agreement with the values obtained by the reference method (based on high-performance liquid chromatography with fluorescence detection/HPLC-FLD). In addition, all samples contained OTA levels lower than the maximum permissible levels. Finally, the proposed strategy allows the use of green analytical chemistry principles; for instance, the use of organic solvents and the generation of waste products were significantly lower than for similar analytical methods reported in the literature.

Advanced determination of the spatial gradient of human health risk and ecological risk from exposure to As, Cu, Pb, and Zn in soils near the Ventanas Industrial Complex (Puchuncaví, Chile).

The townships of Puchuncaví and Quintero, on the coast of central Chile, have soils contaminated by atmospheric deposition of sulfur dioxide and trace elements from the nearby Ventanas Industrial Complex. The purpose of this study was to evaluate potential human health and ecological risks, by determining the spatial distribution of soil total concentrations arsenic (As), copper (Cu), lead (Pb), and zinc (Zn) in these townships. Total concentrations of these elements were determined in 245 topsoil samples, used to generate continuous distribution maps. The background concentrations of Cu, As, Pb, and Zn in the studied soils were 100, 16, 35, and 122 mg kg-1, respectively. The concentrations of Cu, As, and Pb were positively correlated with each other, suggesting that their source is the Ventanas copper smelter. On the other hand, correlations for Zn were weaker than for other trace elements, suggesting low impact of the Ventanas copper smelter on spatial distribution of Zn. Indeed, only 6% of the study area exhibited Zn concentrations above the background level. In contrast, 77, 32 and 35% of the study area presented Cu, As, and Pb concentrations, respectively, above the background level. The carcinogenic risk due to exposure to As was above the threshold value of 10-04 in the population of young children (1-5 years old) on 27% of the study area. These risk values are classified as unacceptable, which require specific intervention by the Chilean government. Based on the estimated concentrations of exchangeable Cu, 10, 15, and 75% of the study area exhibited high, medium, and low phytotoxicity risk, respectively.

Mercury and methylmercury levels in soils associated with coal-fired power plants in central-northern Chile.

Mercury pollution is a worldwide problem, and is associated with a number of natural and anthropogenic processes. The present work, conducted in Chile, a country that has traditionally depended heavily on fossil fuels for power generation, examines total mercury (THg) and monomethylmercury (MMHg) concentrations in soils across different sites exposed to coal fired power plant emissions. Samples from four selected (Renca, Laguna Verde, Las Ventanas, Huasco) and 1 control (Quintay) sites were analyzed using cold vapour and fluorescence spectroscopy (CV-AFS) for THg determination and chromatographic separation with atomic fluorescence detection (DI-GC-AFS) was followed for speciation analysis. From the sites analyzed, Renca and Las Ventanas showed high concentrations of total mercury, exhibiting ranges between 135 - 568 and 94-464 ng g-1 respectively, while Laguna Verde and Huasco exhibited lower values ranged 5-27 and 9-44 ng g-1 respectively. Conversely, analysis of MMHg concentrations showed that only Renca site possessed high values, ranging between 0.1 and 3.0 ng g-1, resulting in this site being considered contaminated. Conversely, other sites showed minimal values comparable to the control site (0.024 ±â€¯0.003 ng g-1) in terms of MMHg concentrations. An analysis of the differences between MMHg and THg concentrations in contaminated sites, suggests an overall absence of methylation in soils of Las Ventanas, probably related to the very high levels of soil heavy metals, especially copper. Moreover, the influence of the composition and physicochemical properties of the different soils on the mobility of the species was assessed. Results obtained (as Log Kd) were 3.5 and 4.1 for Renca and Las Ventanas respectively, suggesting low mobility of mercury species in the environment for both sites. Finally, the data obtained allowed us to establish a first approximation of the differences in concentration and mobility of total and MMHg associated with coal fired power plants emission in central-northern Chile, an area previously understudied in a country heavily dependent on fossil-fuels.

Critical evaluation of third-order advantage with highly overlapped spectral signals. Determination of fluoroquinolones in fish-farming waters by fluorescence spectroscopy coupled to multivariate calibration.

In this work, the analytical performance of a third-order/four-way calibration is evaluated to model a highly overlapped system, where two spectral dimensions are extremely similar, and the results are then compared with the results of second-order/three-way calibration. The four-way data were obtained during the photodegradation of fluoroquinolones (ciprofloxacin, norfloxacin and flumequine) in the form of excitation-emission matrices and modeled by unfolded partial least squares coupled to residual trilinearization (U-PLS-RTL). According to the results, the model obtained with the second-order algorithm (unfolded partial least squares coupled to residual bilinearization: U-PLS-RBL) was unsatisfactory due to high spectral overlap. The third-order approach obtained a satisfactory fit and better figures of merit (LOD, REP, RMSEP, and sensitivity, among others) even in the presence of unexpected interferences due to third-order advantages. Finally, the analytical method based on third-order multivariate calibration was applied to quantify these fluoroquinolones in spiked fish-farming water samples. In this case, the third-order advantage allowed us to satisfactorily model the data and to quantify these compounds in this complex matrix, demonstrating the superior analytical performance of the high-order data that were evaluated.

Critical evaluation of distillation procedure for the determination of methylmercury in soil samples.

In the present work, the efficiency of distillation process for extracting monomethylmercury (MMHg) from soil samples was studied and optimized using an experimental design methodology. The influence of soil composition on MMHg extraction was evaluated by testing of four soil samples with different geochemical characteristics. Optimization suggested that the acid concentration and the duration of the distillation process were most significant and the most favorable conditions, established as a compromise for the studied soils, were determined to be a 70 min distillation using an 0.2 M acid. Corresponding limits of detection (LOD) and quantification (LOQ) were 0.21 and 0.7 pg absolute, respectively. The optimized methodology was applied with satisfactory results to soil samples and was compared to a reference methodology based on isotopic dilution analysis followed by gas chromatography-inductively coupled plasma mass spectrometry (IDA-GC-ICP-MS). Using the optimized conditions, recoveries ranged from 82 to 98%, which is an increase of 9-34% relative to the previously used standard operating procedure. Finally, the validated methodology was applied to quantify MMHg in soils collected from different sites impacted by coal fired power plants in the north-central zone of Chile, measuring MMHg concentrations ranging from 0.091 to 2.8 ng g-1. These data are to the best of our knowledge the first MMHg measurements reported for Chile.

Distribution and pollution assessment of trace elements in marine sediments in the Quintero Bay (Chile).

The aim of this study was to assess the levels of heavy metal pollution in the clay/silt fraction (<63 µm fraction) of marine sediments from Quintero Bay, Chile. For this, sediment samples were collected from 14 sites from the bay and analyzed for major and minor element determination. The metal concentrations found suggest an anthropogenic origin related with Cu, Se, Mo, As, Sb and Pb. The mineralogical characteristics of the samples were determined by XRD and selected samples were examined by SEM to determine morphological differences. The results showed heavy metal-bearing particles such as Cu, Zn, As and Pb, which are most likely associated with by the copper smelter.

Speciation analysis of organotin compounds in human urine by headspace solid-phase micro-extraction and gas chromatography with pulsed flame photometric detection.

A new headspace solid-phase micro-extraction (HS-SPME) method followed by gas chromatography with pulsed flame photometric detection (GC-PFPD) analysis has been developed for the simultaneous determination of 11 organotin compounds, including methyl-, butyl-, phenyl- and octyltin derivates, in human urine. The methodology has been validated by the analysis of urine samples fortified with all analytes at different concentration levels, and recovery rates above 87% and relative precisions between 2% and 7% were obtained. Additionally, an experimental-design approach has been used to model the storage stability of organotin compounds in human urine, demonstrating that organotins are highly degraded in this medium, although their stability is satisfactory during the first 4 days of storage at 4 °C and pH=4. Finally, this methodology was applied to urine samples collected from harbor workers exposed to antifouling paints; methyl- and butyltins were detected, confirming human exposure in this type of work environment.

Distribution of trace elements in particle size fractions for contaminated soils by a copper smelting from different zones of the Puchuncaví Valley (Chile).

Metal contents in soil samples are commonly used to evaluate contamination levels. However, the distribution of metals is dependent on particle size. We investigated the distribution of metals in various particle size fractions of the soil from four sites of the Puchuncaví Valley (Central Chile). The soil samples were segregated into size fractions ranging from 0.3 to 20µm and analyzed using inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of the statistical analysis of the total metal concentrations indicated that the soil samples from Greda and Maitenes, the sites nearest the industrial sources, are the most contaminated. For these sites, the size-fractionated samples containing higher concentrations of Cu, Zn, As, and Pb were found in the finer fractions, suggesting anthropogenic depositions from smelter facilities. In addition, a high Ca concentration was observed in the finer fractions, which could be attributed to the technological approaches used to reduce the SO2 emissions from the roasting process of copper sulfide. The mineral composition of fine particles permitted the identification of Tenorite and Calcium oxide, which are most likely associated with smelting activities, confirming emission of enriched particulate matter from the copper smelter.