Ecological Status of Algeciras Bay, in a Highly Anthropised Area in South-West Europe, through Metal Assessment-Part I: Abiotic Samples.

The ecological status of Algeciras Bay (South-west Europe), highly influenced by anthropogenic activities, was assessed by monitoring Zn, Cd, Pb, and Cu in water and sediment samples. Total contents and metal fractions with different availabilities and their spatial-seasonal distribution were determined. The trend in water and sediment contents were Zn > Pb ≈ Cu > Cd, without significant seasonal variations. Sites 3 and 4, closest to industrial activities, had the highest metal concentrations, mainly in sediments. Cd showed low partition coefficient in water, indicating higher bioavailability. Total metal content in sediments exceeded the threshold effect level for Cu and were close to Pb. The BCR procedure revealed the highest availabilities for Cd and Pb, due to its higher content in exchangeable and reducible fractions. Higher Pb levels (21.4 ± 5.1 mg/kg) were found in sediments of this bay compared with other ecosystems. Pollution indexes for sediment quality revealed that site 3 was the most polluted (CF = 7.12 and Igeo = 2.25). For an integrative study of the ecological status of this significant bay, these results have been complemented with the metal evaluation in benthic and benthopelagic fish tissues in Ecological status of Algeciras Bay, in a highly anthropised area in south-west Europe, through metal assessment-Part II: Biotic samples.

Ecological Status of Algeciras Bay, in a Highly Anthropised Area in South-West Europe, through Metal Assessment-Part II: Biotic Samples.

Biotic samples from Algeciras Bay (South-west Europe) were studied to assess its ecological status, complementing the previous abiotic monitoring of trace metals in water and sediments. This bay is a densely populated area with intense port traffic and is highly industrialised with metal inputs. To study the impact of this, Zn, Cd, Pb, and Cu contents were determined in tissues of benthic (Solea senegalensis) and benthopelagic species (Scorpaena porcus, Trigloporus lastoviza, and Diplodus sargus sargus). Notable levels of Zn and Cu were found in the liver and gills of all fish species. Compared to international muscle guidelines, Pb sometimes exceeded the most restrictive values, outstanding S. porcus with 27% of samples above the permissible value. Metal pollution indexes revealed that the liver and gills of benthic species were more affected by metal pollution than benthopelagic species, especially in most industrialised sites. Particularly, S. senegalensis presented a higher accumulation factor from sediment of Cd and Cu in the liver (30.1 and 345.1), probably due to the close interaction as benthic species. Among the species studied, S. senegalensis and D. sargus sargus proved to be the best representative and useful bioindicators of metal-polluted environments as this bay. The results were consistent with the findings from the abiotic samples.

Induction of Oxidative Stress by Waterborne Copper and Arsenic in Larvae of European Seabass (Dicentrarchus labrax L.): A Comparison with Their Effects as Nanoparticles.

The aim of this work was to compare the potential induction of oxidative stress and the antioxidant enzymatic response after a short-term waterborne exposure to copper (Cu) and arsenic (As) with that of the nanoparticles (NPs) of these elements (Cu-NPs and As-NPs) in fish larvae of the species Dicentrarchus labrax. Larvae were grouped in several tanks and exposed to different concentrations of contaminants (0 to 10 mg/L) for 24 or 96 h under laboratory conditions. Copper and arsenic concentrations were analysed in larval tissues using ICP-MS. A set of oxidative stress biomarkers, including the levels of hydroperoxides (HPs), and superoxide dismutase (SOD) and catalase (CAT) activities were assessed. The trace element concentrations (mg/kg d.w.) in larvae ranged as follows: 3.28-6.67 (Cu at 24 h) and 2.76-3.42 (Cu at 96 h); 3.03-8.31 (Cu-NPs at 24 h) and 2.50-4.86 (Cu-NPs at 96 h); 1.92-3.45 (As at 24 h) and 2.22-4.71 (As at 96 h); and 2.19-8.56 (As-NPs at 24 h) and 1.75-9.90 (As-NPs at 96 h). In Cu tests, the oxidative damage (ROOH levels) was induced from 0.1 mg/L at both exposure times, while for Cu-NPs, this damage was not observed until 1 mg/L, which was paralleled by concomitant increases in SOD activity. The CAT activity was also increased but at lower metal concentrations (0.01 mg/L and 0.1 mg/L for both chemical forms). No oxidative damage was observed for As or As-NPs after 24 h, but it was observed for As after 96 h of treatment with 0.01 mg/L. A decrease in SOD activity was observed for As after 24 h, but it turned out to be increased after 96 h. However, As-NPs did not alter SOD activity. The CAT activity was stimulated only at 96 h by As and at 24 h by As-NPs. Therefore, the two chemical forms of Cu exhibited a higher bioaccumulation and toxicity potential as compared to those of As. Importantly, the association of both Cu and As in NPs reduced the respective trace metal bioaccumulation, resulting also in a reduction in the toxic effects (mortality and biochemical). Furthermore, the assessment of oxidative stress-related biomarkers in seabass larvae appears to be a useful tool for biomonitoring environmental-occurring trace elements.

A Novel Polymer Inclusion Membrane-Based Green Optical Sensor for Selective Determination of Iron: Design, Characterization, and Analytical Applications.

The design, characterization, and analytical application of a green optical sensor for the selective determination of Fe(II) ions is proposed. The sensor is based on the immobilization of the chromogenic reagent picolinaldehyde salicyloylhydrazone (SHPA) within a polymer inclusion membrane. To reduce solvent usage, the reagent was synthesized using a green mechanochemical procedure. The components for sensor preparation were optimized with a sequential simplex method and the optimal composition was found to be 0.59 g cellulose triacetate (base polymer), 0.04 g SHPA (chemosensor reagent), 4.9 mL dibutyl phthalate (plasticizer), and 38 mL dichloromethane (solvent). The conditions of iron analysis were also optimized resulting in pH 6 for aqueous solution, 90 min exposure time and 10 min short-term stability. The optical sensor showed a linear range from the limit of detection (0.48 µmol L-1) to 54 µmol L-1 Fe(II). The precision of the method was found to be 1.44% and 1.19% for 17.9 and 45 µmol L-1 Fe(II), respectively. The characteristics of the sensor allowed the design of a Fe(II)/Fe(III) speciation scheme. The methodology was successfully applied to the determination of iron in food preservatives, food additives, and dietary supplement. Additionally, the Fe speciation scheme was successfully applied to an agricultural fertilizer.

The Role of Intraperitoneal Intraoperative Chemotherapy with Paclitaxel in the Surgical Treatment of Peritoneal Carcinomatosis from Ovarian Cancer-Hyperthermia versus Normothermia: A Randomized Controlled Trial.

BACKGROUND: The treatment of ovarian carcinomatosis with cytoreductive surgery and HIPEC is still controversial. The effect and pharmacokinetics of the chemotherapeutics used (especially taxanes) are currently under consideration. METHODS: A phase II, simple blind and randomized controlled trial (NTC02739698) was performed. The trial included 32 patients with primary or recurrent ovarian carcinomatosis undergoing cytoreductive surgery (CRS) and intraoperative intraperitoneal chemotherapy with paclitaxel (PTX): 16 in hyperthermic (42-43 °C) and 16 in normothermic (37 °C) conditions. Tissue, serum and plasma samples were taken in every patient before and after intraperitoneal chemotherapy to measure the concentration of PTX. To analyze the immunohistochemical profile of p53, p27, p21, ki67, PCNA and caspase-3 and the pathological response, a scale of intensity and percentage of expression and a grouped Miller and Payne system were used, respectively. Perioperative characteristics and morbi-mortality were also analyzed. RESULTS: The main characteristics of patients, surgical morbidity, hemotoxicity and nephrotoxicity were similar in both groups. The concentration of paclitaxel in the tissue was higher than that observed in plasma and serum, although no statistically significant differences were found between the two groups. No statistically significant association regarding pathological response and apoptosis (caspase-3) between both groups was proved. There were no statistically significant differences between the normothermic and the hyperthermic group for pathological response and apoptosis. CONCLUSIONS: The use of intraperitoneal PTX has proven adequate pharmacokinetics with reduction of cell cycle and proliferation markers globally without finding statistically significant differences between its administration under hyperthermia versus normothermia conditions.

Misused terms in analytical chemistry with emphasis on ultrasound application.

A wide number of analytical terms have been applied erroneously for many years by analytical chemists, and they apply at present yet, by considering the time makes their use correct. The question is, may precedents validate the present use of incorrect scientific terms? Misused terms are found along the analytical process, starting with giving the name of the sample to the exiguous fraction of the original sample that reaches the detector or the high-resolution equipment after sample pretreatment and sample preparation. All the steps of the analytical process are considered in this article, with special emphasis on sample preparation and, within this, on the use of ultrasound, mainly for assisting extraction more unequivocally named as leaching or lixiviation. A call of attention in this respect is considered by the author to be of help to the analytical community.

Sensing Cd(II) Using a Disposable Optical Sensor Based on a Schiff Base Immobilisation on a Polymer-Inclusion Membrane. Applications in Water and Art Paint Samples.

A disposable colour-changeable optical sensor based on an interesting polymer inclusion-membrane (PIM) was designed to determine Cd(II) ions in aqueous medium. The Schiff base 2-acetylpyridine benzoylhydrazone (2-APBH) immobilised on the polymer membrane was used as a sensing molecule. The amounts of the PIM components were optimised by a 32 fractional factorial design with two central points and two blocks. The best optical sensor composition consisted of 2.5 g of poly(vinylchloride) (PVC) as a base polymer, 3 mL of tributyl phosphate (TBP) as a plasticiser, and 0.02 g of 2-APBH as a reagent. The sensor showed a good linear response in the range from 0.02 mg L-1 (limit of detection) to 1 mg L-1 of Cd(II) under the following experimental conditions: pH 9.5 (adjusted using ammonium chloride buffer solution at 0.337 mol L-1), 60 min of exposure time plus 2 min of sonication (pulses at 2 s intervals), and 10 min of short-term stability. The relative standard deviation of the method was determined to be 4.04% for 0.4 mg L-1 of Cd(II). The optical sensor was successfully applied to the determination of Cd(II) in natural-water and art-paint samples.

Factors Associated with Serum Vitamin D Metabolites and Vitamin D Metabolite Ratios in Premenopausal Women.

The most representative indicator of vitamin D status in clinical practice is 25(OH)D3, but new biomarkers could improve the assessment of vitamin D status and metabolism. The objective of this study is to investigate the association of serum vitamin D metabolites and vitamin D metabolite ratios (VMRs) with potentially influential factors in premenopausal women. This is a cross-sectional study based on 1422 women, aged 39-50, recruited from a Madrid Medical Diagnostic Center. Participants answered an epidemiological and a food frequency questionnaire. Serum vitamin D metabolites were determined using an SPE-LC-MS/MS platform. The association between participant's characteristics, vitamin D metabolites, and VMRs was quantified by multiple linear regression models. Mean 25(OH)D3 concentration was 49.2 + 18.9 nmol/L, with greater deficits among obese, nulliparous, dark-skinned women, and with less sun exposure. A lower R2 ratio (1,25(OH)2D3/25(OH)D3) and a higher R4 (24,25(OH)2D3/1,25(OH)2D3) were observed in nulliparous women, with high sun exposure, and those with low caloric intake or high consumption of calcium, vitamin D supplements, or alcohol. Nulliparous women had lower R1 (25(OH)D3/Vit D3) and R3 (24,25(OH)2D3/25(OH)D3), and older women showed lower R3 and R4. Vitamin D status modified the association of the VMRs with seasons. VMRs can be complementary indicators of vitamin D status and its endogenous metabolism, and reveal the influence of certain individual characteristics on the expression of hydroxylase enzymes.

Red and White Wine Lees Show Inhibitory Effects on Liver Carcinogenesis.

SCOPE: Wine has shown anticarcinogenic benefits in hepatocarcinoma and polyphenols seem to be responsible for these effects. Wine lees are the sediments produced during fermentation and they endow wine with organoleptic and physicochemical properties. However, the anticarcinogenic role of these compounds is still unknown. Thus, the purpose of this work is to determine the phytochemical profiles of wine lees and then to analyze their anticarcinogenic effect and DNA methylation on a model of hepatocarcinogenesis. METHODS AND RESULTS: The phytochemical composition of lees is determined by the Folin-Ciocalteu method and high-performance liquid chromatography. An in vivo study using a diethyl nitrosamine-hepatocarcinogenesis-induced model is performed to investigate the hepatoprotective properties of different doses of wine lees. For the DNA methylation analysis, a bisulfite-based method is used. Both types of lees mostly contain pyrogallol, gallic, and syringic acid with a high content of catechins in red lees. The carcinogen hypermethylates the Alu-M2 repetitive sequence and white lees decreases the hypermethylation at all tested concentrations. Low concentration of red and white lees and high concentration of white lees significantly improve the hepatocellular architecture and decrease the mitotic index in the murine model. CONCLUSION: These findings suggest that wine lees are promising agents for chemoprevention of hepatocarcinoma.

Plan andino para la prevención y reducción del embarazo en adolescentes con enfoque integral 2017-2022 / ANDEAN PLAN FOR THE PREVENTION AND REDUCTION OF TEENAGE PREGNANCY WITH A COMPREHENSIVE APPROACH 2017-2022

En el marco del problema de salud pública, de derechos humanos y de desarrollo, que constituye el embarazo en adolescentes en América Latina y el Caribe, y de la importancia y necesidad de dar continuidad a las acciones emprendidas por PLANEA 2007, se elabora el presente Plan Andino para la Prevención y Reducción del Embarazo en Adolescentes 2017-2021, el mismo que está organizado en 6 capítulos: 1. Introducción; 2. Contexto regional y Subregional del embarazo en adolescentes; 3. Antecedentes del Plan; 4. Marco referencial de políticas y contexto internacional, así como los principales enfoques transversales que dan sustento a los lineamientos para la prevención del embarazo en adolescentes; 5. Propuesta del Plan con sus líneas estratégicas y la descripción de actividades; 6. Cuadros de seguimiento y evaluación con base a indicadores, se anexan las matrices operativas del Plan; versión elaborada en estrecha coordinación con el Subcomité Andino para la Prevención del Embarazo Adolescente.

Quantitative proteomic analysis of Pseudomonas pseudoalcaligenes CECT5344 in response to industrial cyanide-containing wastewaters using Liquid Chromatography-Mass Spectrometry/Mass Spectrometry (LC-MS/MS).

Biological treatments to degrade cyanide are a powerful technology for cyanide removal from industrial wastewaters. It has been previously demonstrated that the alkaliphilic bacterium Pseudomonas pseudoalcaligenes CECT5344 is able to use free cyanide and several metal-cyanide complexes as the sole nitrogen source. In this work, the strain CECT5344 has been used for detoxification of the different chemical forms of cyanide that are present in alkaline wastewaters from the jewelry industry. This liquid residue also contains large concentrations of metals like iron, copper and zinc, making this wastewater even more toxic. To elucidate the molecular mechanisms involved in the bioremediation process, a quantitative proteomic analysis by LC-MS/MS has been carried out in P. pseudoalcaligenes CECT5344 cells grown with the jewelry residue as sole nitrogen source. Different proteins related to cyanide and cyanate assimilation, as well as other proteins involved in transport and resistance to metals were induced by the cyanide-containing jewelry residue. GntR-like regulatory proteins were also induced by this industrial residue and mutational analysis revealed that GntR-like regulatory proteins may play a role in the regulation of cyanide assimilation in P. pseudoalcaligenes CECT5344. The strain CECT5344 has been used in a batch reactor to remove at pH 9 the different forms of cyanide present in industrial wastewaters from the jewelry industry (0.3 g/L, ca. 12 mM total cyanide, including both free cyanide and metal-cyanide complexes). This is the first report describing the biological removal at alkaline pH of such as elevated concentration of cyanide present in a heterogeneous mixture from an industrial source.

Quantitative method for determination of oleocanthal and oleacein in virgin olive oils by liquid chromatography-tandem mass spectrometry.

Oleocanthal and oleacein, two key secoiridoid derivatives present in virgin olive oil (VOO), are gaining clinical and nutritional interest thanks to their proved bioactivity; therefore, the determination of both phenols is a growing demanded application to increase the value of VOO. The main problem of previously reported liquid chromatography-based methods for oleocanthal and oleacein measurement is their interaction with water or other polar solvents such as methanol to promote the formation of hemiacetal or acetal derivatives. This interaction can occur during either sample extraction, basically liquid-liquid extraction, and/or chromatographic separation. The aim of this research was to evaluate the suitability of LC-MS/MS for absolute quantitation of oleocanthal and oleacein in VOO. For this purpose, both liquid-liquid extraction and chromatographic separation were studied as potential promoters of acetals and hemiacetals formation from oleocanthal and/or oleacein. The results showed that the use of methanol-water solutions for phenols extraction was not influential on the formation of these artifacts. Acetals and hemiacetals from oleocanthal and/or oleacein were only detected at very low concentrations when methanol gradients under acidic conditions were used for chromatographic separation. With this premise, a protocol based on extraction with acetonitrile and a reverse chromatographic gradient with methanol was established to quantify in absolute terms oleocanthal and oleacein in VOO samples. The resulting protocol was applied to three VOO samples characterized by high, medium, and low levels of these two phenols.

Selective ultrasound-enhanced enzymatic hydrolysis of oleuropein to its aglycon in olive (Olea europaea L.) leaf extracts.

Hydrolysis of oleuropein, the main phenol in olive (Olea europaea L.) leaf extracts, to oleuropein aglycon and other subsequent products in the hydrolytic pathway can be catalyzed by different enzymes. Three of the most used hydrolases were assayed to catalyze the process, and ß-glucosidase from Aspergillus niger was selected. Acceleration of the enzymatic hydrolysis by ultrasound (US) was studied using a Box-Behnken design (duty cycle, amplitude, cycle time) and an oleuropein standard, and the optimum US conditions for achieving maximum yield of oleuropein aglycon were 0.5s/s duty cycle, 50% amplitude and 45s cycle. The method was applied to obtain oleuropein aglycon from commercial and laboratory extracts from olive leaves, which may have a pharmacological use as deduced by its healthy properties. The kinetics of the US-assisted enzymatic hydrolysis was monitored by analysis of the target compounds using liquid chromatography-tandem mass spectrometry.

The role of ultrasound in pharmaceutical production: sonocrystallization.

OBJECTIVES: The main aim of this review was to develop a critical discussion of the key role ultrasound (US) can play on the production of active pharmaceutical ingredients (APIs) by discussing the versatile effect this type of energy produces. METHODS: The different crystallization techniques that can be assisted and improved by US are discussed in the light of the available US devices and the effect pursued by application of US energy. Simple and complex analytical methods to monitor API changes are also discussed. KEY FINDINGS: The countless achievements of API US-assisted production are summarized in a table, and outstanding effects such as narrower particle size distribution; decreased particle size, induction time, metastable zone and supersaturation levels; or a solubility increase are critically discussed. CONCLUSIONS: The indisputable advantages of sonocrystallization over other ways of API production have been supported on multiple examples, and pending goals in this field (clarify the effect of US frequency on crystallization, know the mechanism of sonocrystallization, determine potential degradation owing to US energy, avoid calculation of the process yield by determining the concentration of the target drug remaining in the solution, etc.) should be achieved.

Comparative study of the effect of auxiliary energies on the extraction of Citrus fruit components.

A comparative study of methods for ultrasound-assisted extraction (USAE), microwave-assisted extraction (MAE) and superheated liquid extraction (SHLE) of compounds from citrus has been performed. The suited conditions for each method were evaluated to maximize the concentration of 10 representative compounds (sugars, carboxylic acids, phenolic acids and flavonoids) by a desirability function approach based on the chromatographic peaks obtained by LC-DAD. Extracts obtained under the suited conditions were analyzed by LC-QTOF MS/MS. The ANOVA on the molecular entities showed 232 significant entities (p<0.01), and pairwise comparison revealed that USAE and MAE methods are the most similar (50 different entities), and USAE and SHLE the most dissimilar (224 different entities). A discrimination test by PCA showed a clear discrimination among the extraction methods, explaining 78.51% of the total variability. Similarities in the abundance of the monitored compounds was tested by ANOVA showing that the extraction of carboxylic acids (malic and citric acids) was equal by all methods; while for each of the other eight compounds, at least one extraction method is different from the others. Under the evaluated conditions the SHLE method is the less favorable to extract metabolites from citrus, being the best the USAE method.

Composition of fatty acids in virgin olive oils from cross breeding segregating populations by gas chromatography separation with flame ionization detection.

BACKGROUND: Recent technological advances to improve the quality of virgin olive oil (VOO) have been focused on olive breeding programs by selecting outstanding cultivars and target progenies. Fatty acid (FA) composition, with special emphasis on oleic acid (C18:1) and palmitic acid (C16:0), is one of the most critical quality factors to be evaluated in VOO. For this reason, the profile of FAs is frequently used as a decision tool in olive breeding programs. RESULTS: A method based on gas chromatography with flame ionization detection (GC-FID) was used to study the influence of genotype on the concentration of ten of the most important FAs in VOOs from target crosses Arbequina × Arbosana, Picual × Koroneiki and Sikitita × Arbosana and their corresponding genitors Arbequina, Arbosana, Koroneiki, Picual and Sikitita. For this purpose, a targeted approach was selected for determination of esterified FAs (EFAs) and non-esterified FAs (NEFAs) in a dual analysis by the same chromatographic method. A Pearson analysis revealed correlations between pairs of FAs, which allowed detecting metabolic connections through desaturation and elongation enzymes. An ANOVA test (with P < 0.01) led to identification of C16:0 EFA, C16:1 EFA and C18:1 EFA and also C16:1 NEFA and C18:0 NEFA as the FAs more influenced by cross breeding. Statistical analysis was carried out by unsupervised analysis using principal component analysis (PCA) and cluster analysis (CA) to look for variability sources. CONCLUSION: Crosses with a common genitor (Arbequina × Arbosana and Sikitita × Arbosana) were partially overlapped in the PCAs using the profile of FAs. The CA results revealed clear differences between Sikitita × Arbosana and Picual × Koroneiki crosses in the composition of the most significant FAs, while Arbequina × Arbosana was not properly discriminated from the other crosses.

Characterization of monovarietal virgin olive oils by phenols profiling.

The phenolic profiles of seven monovarietal virgin olive oils (VOOs) - viz. Arbequina, Arbosana, Cornicabra, FS-17, Hojiblanca, Picual and Sikitita - were characterized by using a quantitative strategy based on LC-MS/MS and the selected reaction monitoring (SRM) mode. Data dependent methods, based on precursor ion scanning, product ion scanning and neutral loss scanning, were developed for confirmatory analysis of secoiridoid derivatives. The observed phenolic profiles were used to find correlation between pairs of phenols and similarity trends among the monovarietal VOOs. A Pearson analysis revealed several correlations among phenols with p-value<0.01 and correlation coefficient (R)>0.75 in the seven monovarietal VOOs. Cluster analysis showed two main clusters between VOOs, formed by Arbequina/Hojiblanca/Cornicabra/Picual and Sikitita/Arbosana/FS-17. High correlations (R>0.7) were observed for the following pairs of VOOs: Arbequina/Hojiblanca (R=0.77), essentially supported on levels of hydroxytyrosol acetate (3,4-DHPEA-AC) and dialdehydic forms of secoiridoids; Cornicabra/FS-17 (R=0.81) and Picual/FS-17 (R=0.79), by correlation of flavonoids and secoiridoid derivatives in general. The highest correlation was observed for the pair Picual/Cornicabra (R=0.99). This preliminary study allowed setting similarities and dissimilarities between monovarietal VOOs by analysis of the phenolic profile. The observed connections between phenols for different varieties have been tentatively interpreted according to the main pathways for phenols biosynthesis.

Determination of fatty acids and stable carbon isotopic ratio in subcutaneous fat to identify the feeding regime of Iberian pigs.

Discrimination among the types of feeding regimes for Iberian pigs is currently a highly demanded challenge by the Iberian pig sector. In the present research, discrimination among feeding regimes has been achieved by the combination of two analytical methods (based on FAMEs analysis by GC-FID and determination of δ(13)C by IRMS) previously used independently without success. In the present study, 80 samples of adipose tissue from Iberian pigs subjected to four different feedings were analyzed. The study of the variables more influenced by the feeding regime has allowed us to configure panels of markers with predictive power for the studied feedings by multivariate ROC analysis. The results provided values of specificity and sensitivity higher than 85% in most cases. The statistical combination of results from different analytical methods could be the key to develop models for the correct discrimination of Iberian pigs according to the feeding regime.