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The present pilot study was undertaken to investigate the impaired acquired color vision on Calabrian male sample showing this parameter as a biological marker in type 2 diabetes. All patients and controls underwent three pseudo-isochromatic clinical test batteries: Ishihara test, Farnsworth test, and City University test. The results show a specific loss of short-wavelength (blue sensitivity) and typical tritan responses in diabetic patients. Generally, in later stages of the disease, the red-green mechanisms are involved. By the impaired color vision study in diabetic patients, we can confirm the impaired retina-brain cortex pathway. We believe that the above not invasive test analysis can support the other instrumental and imaging analysis to study the impaired retina-brain cortex pathway. Moreover, we think that the present clinical method can be useful in terms of preventive medicine. [ABSTRACT FROM AUTHOR]

European people believed that epilepsy was both a sacred and demoniac disease in the pre- and post-Hippocratic Age, and this belief continued into the Christian era. Epilepsy was wrapped in mystery. The present work shows an epileptic treatment using elk (Alces alces) hoof, which was better known among Northern European people, and explains its historical and popular origins that lead to its importance and success within the Official Medicine in the sixteenth and seventeenth centuries until its gradual decline as a specific treatment in the subsequent centuries. We study authors from both Antiquity and the Modern Age. The present work concludes by highlighting the relationship between epilepsy and its magic-religious inheritance. It could be considered a valid example showing how a popular treatment can earn honors in the Official Pharmacopoeia, but later be excluded. [ABSTRACT FROM AUTHOR]

This work proposes a new method for the quantification of benzothiazoles (BTs), benzotriazoles (BTRs), and benzenesulfonamides (BSAs) in tap water, river water, and wastewater. The protocol involved the use of microextraction by packed sorbent (MEPS), applied for the first time for the extraction of the target analytes, combined with programmed temperature vaporization-gas chromatography-triple quadrupole mass spectrometry (PTV-GC-QqQ-MS). Considering the synergism between MEPS extraction and PTV injection, the experimental variables affecting their performance were simultaneously optimized by "experimental design", while principal component analysis (PCA) was used to find the overall optimal working conditions. Response surface methodology was used to gain a comprehensive understanding of the effects of working variables on method performance. The developed method achieved very good linearities and satisfactory intra- and inter-day accuracies and precisions. The protocol permitted the detection of the target molecules with limit of detection (LODs) values between 0.005 and 0.85 μg/L. The green character of the procedure was evaluated using three metrics: "Analytical Eco-Scale", "Green Analytical Procedure Index" (GAPI), and "Analytical Greenness metric for sample preparation (AGREEprep). The satisfactory results obtained with real water samples demonstrate the applicability of the method for monitoring campaigns and exposome studies. [Display omitted] • A new automatable method for BTs, BTRs, and BSAs quantitation in waters is presented. • MEPS extraction and PTV injection were synergistically optimized by experimental design. • PCA was used to determine the most desirable working condition for maximum sensitivity. • The target compounds were quantified with LODs ranging between 0.005 and 0.85 μg/L. • The "green" character of the procedure was evaluated by greenness metric approaches. [ABSTRACT FROM AUTHOR]

Abstract: Epilepsy is a neurological disorder which has been recognized since antiquity. This paper evaluates the prophylactic and therapeutic remedies used by folk medicine to cure epilepsy in Italy. The data has been collected by reviewing written sources of physicians, ethnographers, folklorists between the late nineteenth and mid twentieth century. This approach leads to unearthing of 78 heterogeneous healing methods that have been divided into 16 (20%) magical, 20 (26%) religious and 42 (54%) natural remedies. The latter has been subdivided into 18 (43%) animal remedies, 17 (40%) plant remedies and 7 (17%) other remedies. Religious and magical remedies were used with the conviction that they would be able to provide recovery from epilepsy and to ward off evil spirits which had taken possession of the sick. Interestingly, the herbal remedies highlighted 12 (70%) plants that play or might play an important role with respect to the mechanisms that generate the epileptic seizures. This leads us to reconsider the historical significance of folk medicine, too often it is underestimated owing to its use of ineffective remedies, born of incompetence and superstition. [Copyright &y& Elsevier]

In Italy, malaria was an endemic disease that was eradicated by the mid-20th century. This paper evaluates the prophylactic and therapeutic remedies used by folk medicine to cure malaria in Calabria (southern Italy). The data has been collected by analysing works of physicians, ethnographers, folklorists and specialists of the study of Calabrian history between the end of the 19th century and the 20th century. The data collected have allowed us to describe the most common cures used by the Calabrian people to treat malaria and the most evident symptoms of this disease, such as intermittent fever, hepato-spleenomegaly, asthenia and dropsy. This approach uncovered a heterogeneous corpus of empirical, magical and religious remedies, which the authors have investigated as evidences of past "expert medicine" and to verify their real effectiveness in the treatment of malaria. [ABSTRACT FROM AUTHOR]

We wish to commemorate Paul Ehrlich on the centennial of his being awarded the Nobel Prize in Physiology or Medicine in 1908. His studies are now considered as milestones in immunology: the morphology of leukocytes; his side-chain theory where he defined the cellular receptor for first time; and his clarification of the difference between serum therapy and chemotherapy. Ehrlich also invented the first chemotherapeutic drug: compound 606, or Salvarsan. We have used some original documents from the Royal Society of London, where Ehrlich was a fellow, and from Leipzig University, where he took a degree in medicine. [ABSTRACT FROM AUTHOR]

Abstract: Objectives: : To determine if the qualitative test (cytochemical) is more reliable than the quantitative test (differential pH-metry) in identifying heterozygous G6PD− subjects. Design and methods: : Identification of heterozygous G6PD− subjects was done by the measurement of G6PD activity and by a cytochemical test. Results: : A cytochemical test is more sensitive than differential pH-metry to identify heterozygous G6PD− subjects. Conclusions: : A cytochemical test is a reliable method for mass screening for G6PD deficiency to identify G6PD− heterozygotes. [Copyright &y& Elsevier]

To determine if measuring the ratio of glucose-6-phosphate dehydrogenase (G6PD) to pyruvate kinase (PK) is more reliable than only measuring G6PD activity to identify heterozygous G6PD− individuals with associated microcytic anemia in the Calabrian population, which shows high frequencies of both the thalassaemia (thal) trait and G6PD deficiency.Measurement of G6PD and PK activities was carried out on 205 samples of whole blood from Calabrian subjects of both sexes (age range 10–50 years) using a double starter differential pH-metry technique.The G6PD/PK ratio is able to differentiate G6PD− heterozygous individuals from the normal population. G6PD/PK values also allowed us to easily identify the G6PD− heterozygous subjects with microcytic anaemia. Student''s t test shows that G6PD/PK ratio is more reliable in both sample groups, relative to G6PD activity in normal subjects.G6PD/PK ratio is a reliable diagnostic parameter for mass screening for G6PD deficiency. [Copyright &y& Elsevier]

The aim of the present work was to ascertain, through the administration of a psychosocial questionnaire, the difficulties that subjects with defective colour vision experience in carrying out everyday tasks and work, including driving a car with a driver's licence held for no more than 3 years. Subjects with defective colour vision ( n = 151) and subjects with normal vision ( n = 302) completed a psychosocial questionnaire regarding the difficulties associated with congenital colour vision deficiency in daily life, work and driving a car. Subjects were diagnosed as colour-blind using the Ishihara test. Statistically significant differences between the two samples were found for daily life activities. Subjects with defective colour vision preferred daytime driving. At night, subjects with defective colour vision had difficulty identifying reflectors on the road and the rear signal lights of cars ahead of them. Colour-blind Calabrian subjects admitted to experiencing colour-related difficulties with a wide range of occupational tasks and leisure pursuits. In particular, colour-blind Calabrian subjects preferred daytime driving, and fewer drove regularly, compared to orthochromatics, who were indifferent to night or daytime driving. [ABSTRACT FROM AUTHOR]

Recognizes Walter Stanborough Sutton as a father of the discipline of Human Genetics. Career background; Awards and achievements; Contribution to human genetics.

• An easy method for polyclyclic aromatic hydrocarbons (PAHs) quantitation in human saliva is presented. • PDMS/DVB/PDMS fiber was used in direct immersion for extraction of thirteen PAHs including low-volatile analytes such as benzo[a]pyrene and dibenzo[a,h]anthracene. • The evaluation of the robustness of fiber coating over time revealed highly satisfactory extraction performance, with no significant drop in signal. • The target compounds were quantified with LLOQs at 100 and 500 ng/L. • The "green" character of the procedure was evaluated by greenness metrics. This work presents a novel method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in saliva samples using solid phase microextraction (SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The protocol utilizes the latest commercially available overcoated fiber (PDMS/DVB/PDMS) for direct immersion extraction of the target analytes, enabling the determination of thirteen PAHs, including low-volatile compounds. The SPME extraction method was optimized using a central composite design (CCD). The evaluation of the fiber coating's robustness over time demonstrated excellent extraction performance with no significant degradation. The validation procedure confirmed good performance for all parameters, with LOQ values (100 ng/L for ten analytes and 500 ng/L for three analytes) comparable to other chromatographic methods. The environmental impact of the protocol was objectively assessed using two recently proposed metrics: the Green Analytical Procedure Index (GAPI) and the Analytical Greenness metric for sample preparation (AGREEprep). Both metrics indicated good overall environmental friendliness, with AGREEprep providing a satisfactory comprehensive score despite the use of highly impactful instrumentation. These characteristics make the developed method suitable for routine analysis in environmental and epidemiological monitoring. [ABSTRACT FROM AUTHOR]

The article discusses the color vision disorder suffered by patients with Parkinson's disease. Topics discussed include the effect of using L-dopa in the management of Parkinson's disease, type and grade of color-blindness, early diagnostic symptoms of the disease, and pattern of retinal impairment of patients.

Bio‐active ethylcellulose (EC) polymeric films have been obtained by incorporating curcumin (curc) and Ag(I)‐based compounds, known for their antioxidant and antimicrobial activity, respectively, within the polymeric matrix. The recently reported Ag(I) coordination polymer, in both its structural forms (α‐[(bpy)Ag(OTf)]∞ and β‐{[(bpy)Ag][OTf]}∞), and the [(bpy)Ag(OTf)]∞‐curc polymeric co‐crystal (bpy=2,2′‐bipyridine; OTf=trifluoromethanesulfonate) have been selected as Ag(I) species. The hybrid composite films have been prepared through the simple solvent casting method and characterized through Powder X‐Ray Diffraction (PXRD), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscope (SEM), UV‐vis spectroscopy. The deep investigation of the film samples highlighted the non‐inert behaviour of EC towards these specific active ingredients. Antimicrobial tests showed that EC films embedding the Ag(I)‐based compounds present good antimicrobial performance, in particular against Staphylococcus aureus, used as a model of Gram‐positive bacteria. In addition, Silver migration tests, performed on the Ag(I)‐incorporating EC films, evidenced low values of silver release particularly in the case of the EC films incorporating [(bpy)Ag(OTf)]∞‐curc. [ABSTRACT FROM AUTHOR]

• An easy method for parabens and bisphenols quantitation in human saliva is presented. • Methyl chloroformate was used as derivatizing reagent. • The entire procedure provides for only 20 µL of organic reagents/solvents. • The target compounds were quantified with LLOQs at 10 and 100 ng/L. • The "green" character of the procedure was evaluated by greenness metrics. The herein presented work aims to the development of an easy method for the quantitative determination of parabens and bisphenols in human salivabased on the use of methyl chloroformate as a derivatizing agent, followed by solid-phase microextraction (SPME) and gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) analysis with selected reaction monitoring (SRM). Using multivariate analysis, two derivatization strategies were compared and optimized, demonstrating that the use of methyl chloroformate led to better sensitivity than the classical derivatization by acetic anhydride. Good performance in the sorption process of the derivatized target analytes was obtained using the most recent commercialized overcoated fiber (PDMS/DVB/PDMS). The validation procedure of the final protocol led to satisfactory results in terms of linearity, limit of quantitation, accuracy, and precision. All parabens were quantified from 10 ng/L using the developed method, except for methylparaben, which was quantified from 100 ng/L along with all bisphenols. Intra- and inter-day accuracy and intra- and inter-day precision can be considered satisfactory for all analytes (values between 73% and 118%), except for the inter-day accuracy of BPF. Quite good results also in terms of matrix effect were obtained for the target compounds (range 71% to 118%, RSD% less than 13.6%), except for BPA at the middle concentration and MeP at the lowest concentration. The greenness of the method was evaluated and the results indicated that our approach is more eco-friendly than previously published methods. Based on its characteristics, the presented method can be considered a suitable approach to determine parabens and bisphenols in routine analysis for biomonitoring purposes. [ABSTRACT FROM AUTHOR]

The article offers information on the engraving named "The Syphilitic" by the German Renaissance artist Albrecht Dürer.

The article offers information regarding the prevalence of syphilis in different countries in Europe.

This article discusses the representation of syphilis and jealousy in Agnolo Bronzino's painting "Allegory of Venus and Cupid."

Lead (Pb), due to its high toxicity and bioaccumulation tendency, is one of the top three pollutants of concern for both humans and wildlife and occupies second place in the Priority List of Hazardous Substances. In freshwater fish, Pb is mainly absorbed through the gills, where the greatest accumulation occurs. Despite the crucial role of gills in several physiological functions such as gas exchange, water balance, and osmoregulation, no studies evaluated the effects of environmentally relevant concentrations of Pb on this organ, and existing literature only refers to high levels of exposure. Herein we investigated for the first time the molecular and morphological effects induced by two low and environmentally relevant concentrations of Pb (2.5 and 5 μg/L) on the gills of Danio rerio, a model species with a high translational value for human toxicity. It was demonstrated that Pb administration at even low doses induces osmoregulatory dysfunctions by affecting Na+/K+-ATPase and AQP3 expression. It was also shown that Pb upregulates MTs as a protective response to prevent cell damage. Modulation of SOD confirms that the production of reactive oxygen species is an important toxicity mechanism of Pb. Histological and morphometric analysis revealed conspicuous pathological changes, both dose- and time-dependent. [ABSTRACT FROM AUTHOR]

Pendimethalin-based herbicides are used worldwide for pre-emergence selective control of annual grasses and weeds in croplands. The endurance of herbicides residues in the environment has an impact on the soil biodiversity and fertility, also affecting non-target species, including terrestrial invertebrates. Carabid beetles are known as natural pest control agents in the soil food web of agroecosystems, and feed on invertebrates and weed seeds. Here, a mass spectrometry untargeted profiling of haemolymph is used to investigate Pterostichus melas metabolic response after to pendimethalin-based herbicide exposure. Mass spectrometric data are examined with statistical approaches, such as principal component analysis, for possible correlation with biological effects. Those signals with high correlation are submitted to tandem mass spectrometry to identify the associated biomarker. The time course exposure showed many interesting findings, including a significant downregulation of related to immune and defense peptides (M-lycotoxin-Ls4a, Peptide hormone 1, Paralytic peptide 2, and Serine protease inhibitor 2). Overall, the observed peptide deregulations concur with the general mechanism of uptake and elimination of toxicants reported for Arthropods. [ABSTRACT FROM AUTHOR]

Equilibriaoccurring between 2-hydroxybenzoic acid (salicylic acid,H2L) and calcium(II), magnesium(II), and nickel(II) havebeen studied by potentiometric titrations with glass electrodes at298.15 K in self-medium constituted of 1.05 mol·kg–1NaHL. The self-medium composition can be considered constant sinceonly a small amount of ligand HL–is transformedin the reaction products. The hydrogen ion concentration was variedfrom 10–2mol·kg–1to incipientprecipitation of a basic salt of each metal, whose formation dependson the particular metal. The total metal concentration, CM, ranged from 3.05·10–3mol·kg–1to 10.01·10–3mol·kg–1. The higher CMvaluewas imposed in order to avoid changes in the ionic medium and in theactivity coefficients. The experimental data have been explained byassuming the formation of the complexes: CaL; MgL, MgL22–, and MgL34–; NiLand NiL22–. [ABSTRACT FROM AUTHOR]

Ptaquiloside (Pta) is a potent carcinogen present in bracken fern and in soil matrices, that can potentially leach to the aquatic environment. More recently its presence in the milk of different farm animals has been reported. Pterosin B (Ptb) and bromopterosin (BrPt) represent the most convenient analogues in the detection of ptaquiloside by mass spectrometry. Pterosin sesquiterpenes are also involved in many patented biomedical protocols. In this work we introduce a new and convenient approach to the synthesis in three steps and more than 80% yield of d4-pterosin B (d4-Ptb) and d4-bromopterosin (d4-BrPt), useful as internal standards in the quantification of ptaquiloside. [ABSTRACT FROM AUTHOR]

The mercury removal efficiency of a novel metal‐organic framework (MOF) derived from the amino acid S‐methyl‐L‐cysteine is presented and the process is characterized by single‐crystal X‐ray crystallography. A feasibility study is further presented on the performance of this MOF—and also that of another MOF derived from the amino acid L‐methionine—when used as the sorbent in mixed matrix membranes (MMMs). These MOF‐based MMMs exhibit high efficiency and selectivity—in both static and dynamic regimes—in the removal of Hg2+ from aqueous environments, due to the high density of thioalkyl groups decorating MOF channels. Both MMMs are capable to reduce different concentration of the pollutant to acceptable limits for drinking water (<2 parts per billion). In addition, a novel device, consisting of the recirculation and adsorption of contaminated solutions through the MOF–MMMs, is designed and successfully explored in the selective capture of Hg2+. Thus, filtration of Hg2+ solutions with multiple passes through the permeation cell shows a gradual decrease of the pollutant concentration. These results suggest that MOF‐based MMMs can be implemented in water remediation, helping to reduce either contaminants from accidental unauthorized or deliberate metal industrial dumping and to ensure access for clean and potable freshwater. [ABSTRACT FROM AUTHOR]

The aim of this work was to analyze the potential of reverse osmosis (RO) membranes in the recovery and concentration of aroma compounds from orange juice evaporator condensate (EC) streams. Concentration experiments were performed by using three RO spiral-wound aromatic polyamide membranes (SG1812C-34D, SC1812C-34D and SE1812) with different NaCl rejections. The effect of transmembrane pressure, axial feed flowrate and volume concentration ratio (VCR) on permeate flux was studied. Rejections of the investigated membranes towards specific aroma compounds (octanol, α-terpineol, terpinen-4-ol, cis-carveol, karvon, linalool) in selected operating conditions were also evaluated. The concentrations of the aroma compounds were determined by gas chromatography coupled with mass spectrometry (GC-MS) using headspace solid-phase microextraction (HS-SPME) as a sample preparation approach. For all selected membranes, the permeate flux increased linearly by increasing the operating pressure from 5 to 25 bar; on the other hand, the feed flowrate did not have any significant effect on the permeate flux. High retention values towards aroma compounds (>80%) were measured for all selected membranes. However, the SC membrane showed the highest rejection values (>96%) and the best correlation between concentration factor of aroma compounds and VCR. [ABSTRACT FROM AUTHOR]

In the following work, a new method for the analysis of the phthalate monoesters in human urine was reported. Phthalate monoesters are metabolites generated as a result of phthalate exposure. In compliance with the dictates of Green Analytical Chemistry, a rapid and simple protocol was developed and optimized for the quantification of phthalate monoesters (i.e., monoethyl phthalate, monoisobutyl phthalate, mono‐n‐butyl phthalate, mono‐(2‐ethylhexyl) phthalate, mono‐n‐octyl phthalate, monocyclohexyl phthalate, mono‐isononyl phthalate) in human urine, which entails preceding derivatization with methyl chloroformate combined with the use of commercial solid phase microextraction and the analysis by gas chromatography‐triple quadrupole mass spectrometry. The affinity of the derivatized analytes toward five commercial coatings was evaluated, and in terms of analyte extraction, the best results were reached with the use of the divinylbenzene/carboxen/polydimethylsiloxane fiber. The multivariate approach of experimental design was used to seek for the best working conditions of the derivatization reaction and the solid phase microextraction, thus obtaining the optimum response values. The proposed method was validated according to the guidelines issued by the Food and Drug Administration achieving satisfactory values in terms of linearity, sensitivity, matrix effect, intra‐ and inter‐day accuracy, and precision. [ABSTRACT FROM AUTHOR]

Particulate matter (PM) is among the most dangerous air pollutants, and there is a growing concern related to the effects of airborne particles on human health. Their harmful effects can be derived are directly linked to the size of particles themselves and the associated pollutants after they have been taken up by inhalation. In this work was developed a new analytical method for the quantification of organophosphorus esters (OPE) bound to airborne PM. The proposed protocol provides for the microwave-assisted extraction (MAE) of the analytes from the PM followed by solid-phase microextraction gas chromatography-tandem mass spectrometry determination (SPME-GC-MS/MS). Unlike to the traditional protocol, which provides for the use of tedious Soxhlet extraction with environmentally damaging organic solvents, the proposed method allows for a reliable quantification by using an eco-friendly hydroalcoholic mixture (water/ethanol; 50:50, v/v). The method was developed using as target compounds ten organophosphate esters, namely tripropyl phosphate (TPP), tri-n-butyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tributoxyethyl phosphate (TBEP), triphenyl phosphate (TPhP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP) and tricresyl phosphate (TCP). The extraction performance of five SPME fibers was evaluated and the DVB/CAR/PDMS coating demonstrated to be the most suitable for the extraction of the target analytes. Experimental Design was used for the multivariate optimization of the parameters affecting the MAE process as well as the SPME extraction, and the optimal working conditions were determined by using Derringer's desirability function. The developed method was validated in terms of linearity, sensitivity (LLOQ values of 0.5 ng/mL for TDCPP and 0.1 ng/mL for the other analytes), matrix effect (81–117%), intra and inter day accuracy (83–115% and 80–115%, respectively), and precision (repeatability and reproducibility in the range 1.0–12.4% and 2.3–15.2%, respectively). The satisfactory performances reached make the proposed protocol a green and high-throughput alternative for OPE quantification in particulate matter. [ABSTRACT FROM AUTHOR]

Polyamines are aliphatic amines with low molecular weight that are widely recognized as one of the most important cancer biomarkers for early diagnosis and treatment. The goal of the work herein presented is the development of a rapid and simple method for the quantification of free polyamines (i.e., putrescine, cadaverine, spermidine, spermine) and N -monoacetylated polyamines (i.e., N 1 -Acetylspermidine, N 8 -Acetylspermidine, and N 1 -Acetylspermine) in human urine. A preliminary derivatization with propyl chloroformate combined with the use of solid phase microextraction (SPME) allowed for an easy and automatable protocol involving minimal sample handling and no consumption of organic solvents. The affinity of the analytes toward five commercial SPME coatings was evaluated in univariate mode, and the best result in terms of analyte extraction was achieved using the divinylbenzene/carboxen/polydimethylsiloxane fiber. The variables affecting the performance of SPME analysis were optimized by the multivariate approach of experimental design and, in particular, using a central composite design (CCD). The optimal working conditions in terms of response values are the following: extraction temperature 40 °C, extraction time of 15 min and no addition of NaCl. Analyses were carried out by gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) in selected reaction monitoring (SRM) acquisition mode. The developed method was validated according to the guidelines issued by the Food and Drug Administration (FDA). The satisfactory performances reached in terms of linearity, sensitivity (LOQs between 0.01 and 0.1 μg/mL), matrix effect (68–121%), accuracy, and precision (inter-day values between −24% and +16% and in the range 3.3–28.4%, respectively) make the proposed protocol suitable to be adopted for quantification of these important biomarkers in urine samples. [ABSTRACT FROM AUTHOR]

Abstract: In this work, a polydimethylsiloxane/divinylbenzene fiber overcoated with a layer of polydimethylsiloxane was evaluated as analytical sampling tool for the first time in human urine. Urinary polycyclic aromatic hydrocarbons with 2–6 aromatic rings were considered as target compounds. The analyte uptake in kinetic and thermodynamic regime was evaluated and compared to the performances of polydimethylsiloxane/divinylbenzene and polydimethylsiloxane fibers. The assessment of the robustness and endurance of the overcoated fiber was carried out by direct immersion solid‐phase microextraction in undiluted urine performing up to 120 consecutive extractions. The overcoated fiber was then used to develop a fast and easy direct immersion solid‐phase microextraction with gas chromatography and triple quadrupole mass spectrometry protocol for the quantification of the target polycyclic aromatic hydrocarbons. The attained values of accuracy and precision were 75–114% and 2–19%, respectively, while the limits of quantification ranged between 0.05 and 1 ng/L. The proposed protocol was applied to the screening of urine samples collected from smoking and nonsmoking volunteers. The successful results obtained by using the overcoated fiber create not only new alternatives for polycyclic aromatic hydrocarbon exposure assessment but also new perspectives for the application of direct immersion solid‐phase microextraction to the analysis of bioclinical matrixes. [ABSTRACT FROM AUTHOR]

In this work, organophosphate ester flame retardant (OPFRs) assay in environmental waters was addressed by using microextraction by packed sorbent (MEPS) and gas chromatography-tandem mass spectrometry (GC-MS/MS). Ten OPFRs with different physicochemical properties were taken into account as target compounds for a comprehensive method evaluation. Five MEPS cartridges (i.e., C2, C8, C18, Silica, and DVB) and seven solvents (i.e., methanol, ethyl acetate, methyl tert-butyl ether, hexane, acetonitrile, dichloromethane, and trichloromethane) were surveyed. The analysis was performed by using a gas chromatograph equipped with a programmed temperature vaporization injector (PTV). Univariate and multivariate approaches were exploited in order to optimize the parameters affecting the MEPS extraction and the PTV injection of the analytes into the gas chromatographic system. The optimal working conditions were achieved using DVB as sorbent material and acetonitrile as elution solvent. Internal standard calibration was carried out using TBP-d27 and TCEP-d12. Satisfactory values of accuracy and precision were generally obtained as well as limit of detection (2.7-99 pg/mL for tap water; 2.9-97 pg/mL for river water; 3-107 pg/mL for wastewater) and limit of quantification (0.01-0.2 ng/mL). The proposed protocol was evaluated on real case scenarios by analyzing tap water, river water and simulated wastewater samples. The developed method is not only eco-friendly due to the low use of organic solvents but also simple and automatable since the MEPS extraction procedure can be implemented in the autosampler routine. [ABSTRACT FROM AUTHOR]

A novel approach for the rapid discrimination of bergamot essential oil from other citrus fruits oils is presented. The method was developed using paper spraymass spectrometry (PS-MS) allowing for a rapid molecular profiling coupled with a statistic tool for a precise and reliable discrimination between the bergamot complex matrix and other similar matrices, commonly used for its reconstitution. Ambient mass spectrometry possesses the ability to recordmass spectra of ordinary samples, in their native environment, without sample preparation or pre-separation by creating ions outside the instrument. The present study reports a PS-MS method for the determination of oxygen heterocyclic compounds such as furocoumarins, psoralens and flavonoids present in the non-volatile fraction of citrus fruits essential oils followed by chemometric analysis. The volatile fraction of Bergamot is one of the most known and fashionable natural products, which found applications in flavoring industry as ingredient in beverages and flavored foodstuff. The development of the presented method employed bergamot, sweet orange, orange, cedar, grapefruit and mandarin essential oils. PS-MS measurements were carried out in full scan mode for a total run time of 2 min. The capability of PS-MS profiling to act as marker for the classification of bergamot essential oils was evaluated by using multivariate statistical analysis. Two pattern recognition techniques, linear discriminant analysis and soft independent modeling of class analogy, were applied to MS data. The cross-validation procedure has shown excellent results in terms of the prediction ability because both models have correctly classified all samples for each category. [ABSTRACT FROM AUTHOR]

Four class-modeling techniques (soft independent modeling of class analogy (SIMCA), unequal dispersed classes (UNEQ), potential functions (PF), and multivariate range modeling (MRM)) were applied to multielement distribution to build chemometric models able to authenticate chili pepper samples grown in Calabria respect to those grown outside of Calabria. The multivariate techniques were applied by considering both all the variables (32 elements, Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Fe, Ga, La, Li, Mg, Mn, Na, Nd, Ni, Pb, Pr, Rb, Sc, Se, Sr, Tl, Tm, V, Y, Yb, Zn) and variables selected by means of stepwise linear discriminant analysis (S-LDA). In the first case, satisfactory and comparable results in terms of CV efficiency are obtained with the use of SIMCA and MRM (82.3 and 83.2% respectively), whereas MRM performs better than SIMCA in terms of forced model efficiency (96.5%). The selection of variables by S-LDA permitted to build models characterized, in general, by a higher efficiency. MRM provided again the best results for CV efficiency (87.7% with an effective balance of sensitivity and specificity) as well as forced model efficiency (96.5%). [ABSTRACT FROM AUTHOR]

Heavy metal contamination is recognized worldwide as a serious threat to human health and wildlife, and reducing their emissions is a priority of international and EU actions. Due to its persistence, high bioaccumulation tendency, and toxicity properties, lead (Pb) is one of the heavy metals of greatest concern. Even at low concentrations, lead induces various clinical and subclinical conditions in both humans and animals, and it has been included in the priority list of hazardous substances. In the present study, we used zebrafish's early stages as a model, given their well-acknowledged predictive value in the risk assessment of chemicals. This study was designed to investigate the morphological and morphometric alterations induced by Pb during zebrafish's early development and disclose the putative effects stage- and/or dose-dependent. We examined injuries induced by two environmentally relevant and extremely low concentrations of Pb (2.5 μg/L and 5 μg/L) during two exposure windows: early (between 1 and 7 dpf) and late (between 2 and 8 dpf). We clearly demonstrated that the incidence and severity of morphological abnormalities increased with increasing Pb dose and exposure time in both early and late-exposed groups. Furthermore, we revealed that malformation severity was significantly higher in the early exposed group than in the late exposure group at all exposure times and for both tested doses, thus highlighting the high sensitivity of zebrafish during the initial stages of development. The information presented in this paper emphasizes the effectiveness of morphological biomarkers in unveiling threatening situations and supports the role of zebrafish embryos and larvae in risk assessment and environmental monitoring. [Display omitted] • Low Pb doses induce morphological alterations in developing zebrafish. • Abnormalities appear after short-term exposure in all experimental groups. • The frequency and severity of injuries increased with increasing dose and time. • The degree of injuries is higher in early-exposed animals. • Specific target organ alterations depend on dose/stage. [ABSTRACT FROM AUTHOR]

Hydrophilic porous polyethersulfone (PES) membranes and microcapsules were prepared via Non-Solvent Induced Phase Separation (NIPS) with the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) as structure control agent, added to the conventionally employed PVPK17 pore former. The introduction of [BMIM][PF6] affects the phase inversion mechanism, resulting in different morphologies of the materials. Optimal conditions for the preparation of membranes (ILMs) were: 10-15 wt.% PES, 0-4 wt.% PVPK17, 5-25 wt.% [BMIM][PF6], while slightly different conditions were applied for the preparation of microcapsules (ILMCs): 10% wt.% PES, 0-4% wt.% PVPK17, and 5-15 wt.% [BMIM][PF6]. Thus, the produced porous spongy microcapsules (average diameter ∼800 μm) and flat sheet ionic liquid membranes (ILMs) were characterized by electronic microscopy (SEM), FTIR and Raman spectroscopy and thermal analysis. [BMIM][PF6] concentration is a key factor for controlling the internal membrane morphology. Indeed, higher concentrations of [BMIM][PF6] additive increases the viscosity of casting solution and reduces solvent exchange speed, thereby altering the membrane morphology from a channelled structures (finger-like) to a spongy type. [ABSTRACT FROM AUTHOR]

Desorption electrospray ionization mass spectrometry (DESI-MS) and easy ambient sonic-spray ionization mass spectrometry (EASI-MS) are employed here in the forensic analysis of chemical compounds found in condoms and relative traces, and their analytical performances are compared. Statistical analysis of data obtained from mass spectra only was applied in order to obtain classification rules for distinguishing ten types of condoms. In particular, two supervised chemometric techniques [linear discriminant analysis (LDA) and soft independent modeling of class analogy (SIMCA)] were carried out on absolute and relative intensity values to test the performances of statistical models in terms of predictive capacity. The achieved classification of samples was excellent because of the high prediction percentages of the method used both for DESI and EASI mass spectrometry analyses, confirming these two as potential ambient ionization techniques for forensic analyses in case of sexual assault crimes. EASI-MS showed 99% prediction ability for LDA using relative data and 100% prediction ability for SIMCA using both absolute and relative ones, while DESI showed 94% prediction ability for both LDA and SIMCA. The absence of any sample preparation technique gives advantages in terms of sample preservation and reduced contamination, allowing successive analyses to be performed on the same sample by other techniques. [ABSTRACT FROM AUTHOR]

Highlights: [•] A new SPME-GC-QqQ MS approach was developed for the determination of hydrazine in drinking water at trace levels. [•] Multivariate optimization was performed on derivatization reaction, mass spectrometry conditions and SPME parameters. [•] SRM acquisition by GC-QqQ-MS instrument enhances the ability in analyte quantification. [ABSTRACT FROM AUTHOR]

Highlights: [•] Benzothiazoles, benzotriazoles and benzosulfonamides determination in aqueous matrices. [•] New environmental-friendly and high-throughput protocol developed by SPME-GC–QqQMS. [•] Sample preparation strategy completely avoids the use of organic solvents. [•] MRM acquisition by GC–QqQ-MS instrument enhances analytes identification ability. [Copyright &y& Elsevier]

Highlights: [•] A SPME-GC–QqQ MS approach was developed for the quantification of dopamine, serotonin and norepinephrine in human urine. [•] The presence of organic solvents in the final protocol was minimized by the combined use of alkyl chloroformate and SPME. [•] SRM acquisition by GC–QqQ-MS instrument enhances the ability in analytes identification. [Copyright &y& Elsevier]

Cd(II)-, Pb(II)- and Zn(II)-cystine complexes were investigated by potentiometric and different mass spectrometric (MS) methodologies. Laser desorption mass spectrometry has provided both the composition and structure of metal-cystine complexes according to the speciation models proposed on the basis of the potentiometric data. Detection of neutral complexes was achieved by protonation or electrochemical reduction during mass spectrometric experiments. The redox activity of metal-cystine complexes was confirmed by laser desorption and charge transfer matrix assisted laser assisted MS experiments, which allowed us to observe the formation of complexes with a reduction of cystine. The stoichiometry of Cd(II)-, Pb(II)- and Zn(II)-cystine complexes was defined by observing the isotopic pattern of the investigated compound. The results suggest that interaction occurs through the carboxylate group of the ligand. [ABSTRACT FROM AUTHOR]

A new analytical approach, using paper spray tandem mass spectrometry, has been developed for assay of carnitine and acylcarnitines in urine. Paper spray (PS) is a very promising technique, especially in clinical investigations, because of its simplicity, low cost, and rapid sample preparation. A home-made paper spray device was used for assay of urinary acylcarnitines (C2-C18). The performance of solvents with different elution efficiency and paper substrates with different porosity grade and structure were tested by use of spiked synthetic urine. Tandem mass spectrometry in multiple reaction monitoring (MRM) mode was optimized to obtain better specificity and sensitivity. Analyte signals were evaluated for stability and reproducibility. Calibration with [H]propionylcarnitine (C3-d3), [H]octanoylcarnitine (C8-d3), and [H] palmitoylcarnitine (C16-d3) as internal standards was used for quantification. Very good linearity was obtained, with correlation coefficients >0.99 for C0-C12 and C16 acylcarnitines and >0.96 for C14 and C18 acylcarnitines. Accuracy and precision (RSD, %) of the proposed procedure were tested at concentrations of 0.8, 8, and 20 mg L with very satisfactory results: overall mean accuracy was 98.9 % and overall mean relative standard deviation 1 %. Limits of detection (LOD) between 6 and 208 μg L for propionylcarnitine and tetradecanoylcarnitine, respectively, can be regarded as very satisfactory. Application of the method to real urine proved that paper spray tandem mass spectrometry is a simple, rapid, and direct tool (no derivatization is required) for assay of carnitine and C2-C12 acylcarnitines in urine. [ABSTRACT FROM AUTHOR]

Abstract: Homovanillic acid (HVA), vanylmandelic acid (VMA), and 5-hydroxyindoleacetic acid (5-HIAA) are the metabolites of some catecholamines such as epinephrine, nor-epinephrine, dopamine and serotonin and their quantification is used in the diagnosis and management of patients with neurocrine tumors. A novel approach in the assay of these biomarkers in human urine samples by solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC–QqQ-MS) is presented. A preliminary derivatization with ethyl chloroformate/ethanol was used and the corresponding derivatives were then extracted by SPME in immersion mode. The performance of five SPME fibers and three chloroformates were evaluated in univariate mode and the best results were obtained using the polyacrylate fiber and ethyl chloroformate. The variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of “Experimental design” and, in particular, a central composite design (CCD) was applied. The optimum working conditions in terms of response values were achieved by performing analysis at room temperature with addition of NaCl (9.5%) and with an extraction time of 25.8min. Identification and quantification of analytes were carried out by using a gas chromatography-triple quadrupole mass spectrometry (GC–QqQ MS) system in multiple reaction monitoring (MRM) acquisition. An evaluation of all analytical parameters shows that the proposed method provides satisfactory results. Very good linearities were, in fact, achieved in the tested calibration ranges with correlation coefficient values >0.99 for all the analytes and accuracies and RSDs calculated for between-run and tested at concentrations of 1, 10, and 80mgL−1 were ranging from 91.3% to 106.6%, and from 0.5 to 8.9%, respectively. Moreover, the LOD values obtained can be considered very satisfactory (1.3, 0.046 and 24.3μgL−1 for HVA, VMA and 5-HIAA, respectively). The developed protocol represents, therefore, a simple, rapid and selective tool for assaying these acidic biomarkers in urine samples for neuroendocrine cancer diagnosis. [Copyright &y& Elsevier]

Abstract: In plants, the aroma imprint is expressed through well-established and constant ratios between different compounds, which mainly develop through the Lipoxygenase pathway. Such imprint strongly relies on plant genetic traits but can be modulated by exogenous environmental factors. In order to enlarge knowledge on the genetic control underlying aroma biogenesis in olive (Olea europaea L.) drupes, in the present study we characterized one member of ALCOHOL DEHYDROGENASE gene family. The ALCOHOL DEHYDROGENASE activities act along Lipoxygenase enzymatic cascade by interconverting aldehydes into alcohols. The temporal expression pattern of O. europaea ALCOHOL DEHYDROGENASE was monitored by quantitative Real Time-Polymerase Chain Reaction in drupes at different developmental stages (i.e. from light green phase to ripening stage) of two olive cultivars widely used for olive and oil production. The expression of a known LIPOXYGENASE gene (ACG56281.1) was jointly monitored as marker of drupe development. Results were analysed in relation to the spectrum of volatile compounds developed from crushed drupes estimated by Solid-Phase Micro-Extraction method in-line with a Gas Chromatograph/ion trap Mass Spectrometer. The obtained results showed that both cultivar and maturation stage impact on the expression of O. europaea ALCOHOL DEHYDROGENASE gene which in the pathway is co-ordinately modulated with LIPOXYGENASE expression. The transcriptional differences between cultivars appeared to be related to variation of metabolite contents at early developmental stages. The joint role of genes acting in the Lipoxygenase pathway as molecular markers for flavour characteristic of olive drupes is discussed. [Copyright &y& Elsevier]

Abstract: A new analytical approach is exploited in the assay of selenium speciation in selenized and not selenium enriched potatoes based on the widely available solid-phase microextraction (SPME) coupled to-GC–triple quadrupole mass spectrometry (SPME-GC–QqQ MS) method. The assay of selenomethionine (SeMet) and selenomethylselenocysteine (SeMeSeCys) in potatoes here reported provides clues to the effectiveness of SPME technique combined with gas chromatography–tandem mass spectrometry, which could be of general use. For the exploitation of the GC method, the selected analytes were converted into their N(O,S)-alkoxycarbonyl alkyl esters derivatives by direct treatment with alkyl chloroformate in aqueous extracts. The performance of five SPME fibers and three chloroformates were tested in univariate mode and the best results were obtained using the divinylbenzene/carboxen/polydimethylsiloxane fiber and propylchloroformate. The variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of design of experiment (DoE) and, in particular, a central composite design (CCD) was applied. Tandem mass spectrometry in selected reaction monitoring (SRM) has allowed the elimination of matrix interferences, providing reconstructed chromatograms with well-resolved peaks and the achievement of very satisfactory detection and quantification limits. Both precision and recovery of the proposed protocol tested at concentration of 8 and 40μgkg−1 (dry matter), offered values ranging from 82.3 to 116.3% and from 8.5 to 13.1% for recovery and precision, respectively. The application of the method to commercial samples of selenized and not selenium enriched potatoes proved that the Se fertilization increases significantly the concentration of these bioavailable selenoamino acids. [Copyright &y& Elsevier]

Abstract: A simple and sensitive method was developed for the quantification of five carbamate pesticides in water samples using solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The performance of five SPME fibers was tested in univariate mode whereas the other variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of design of experiment (DoE) and, in particular, a central composite design (CCD) was applied. The optimum working conditions in terms of response values were achieved by performing analysis with polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber in immersion mode for 45min at room temperature with addition of NaCl (10%). The multivariate chemometric approach was also used to explore the chromatographic behavior of the carbamates and to evaluate the importance of each variable investigated. An overall appraisement of results shows that the factor which gave a statistically significant effect on the response was only the injection temperature. Identification and quantification of carbamates was performed by using a gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) system in multiple reaction monitoring (MRM) acquisition. Since the choice of internal standard represented a crucial step in the development of method to achieve good reproducibility and robustness for the entire analytical protocol, three compounds (2,3,5-trimethacarb, 4-bromo-3,5-dimethylphenyl-n-methylcarbamate (BDMC) and carbaryl-d7) were evaluated as internal standards. Both precision and accuracy of the proposed protocol tested at concentration of 0.08, 5 and 3μgl−1 offered values ranging from 70.8% and 115.7% (except for carbaryl at 3μgl−1) and from 1.0% and 9.0% for accuracy and precision, respectively. Moreover, LOD and LOQ values ranging from 0.04 to 1.7ngl−1 and from 0.64 to 2.9ngl−1, respectively, can be considered very satisfactory. [Copyright &y& Elsevier]

Abstract: The work aims at developing a rapid and sensitive method for the quantification of perfluorocarboxylic acids in aqueous matrices. The proposed analytical approach is based on the use of solid phase microextraction in headspace mode after a fast derivatization of the carboxylate function by propylchloroformate/propanol mixture. Several fibers were evaluated and the optimization of the parameters affecting the SPME process was carried out using a central composite design. The optimum working conditions in terms of response values were achieved by performing analysis with CAR/PDMS fiber at room temperature, without addition of NaCl, with a sample volume of 6ml and an extraction time of 10min. Assay of PFCAs was performed by using a gas chromatography–triple quadrupole mass spectrometry (GC–QqQ MS) system in negative chemical ionization mode with ammonia as reagent gas. An overall evaluation of all analytical parameters shows that the proposed method provides satisfactory results. In particular, the observed accuracies, ranging from 84.4% to 116.8%, and the RSD values in the range 0.4% and 14.5% confirm the effectiveness of the developed protocol in the assay of PFCAs content in aqueous matrices. Moreover, LOD and LOQ values ranging from 0.08 to 6.6ngl−1 and from 0.17 to 14.3ngl−1, respectively, can be considered very satisfactory. None of the compounds were detected in six samples of river collected in Calabria. [Copyright &y& Elsevier]

Sarcosine is an amino acid derivative of N-methylglycine and is involved in the amino acid metabolism and methylation processes that are enriched during prostate cancer progression. It could also serve as a new target to be measured during therapeutic interventions and help in the identification of aggressive tumors for radical treatment. In this study, we present a new urine test that can help early diagnosis of prostate cancer. The method for the quantification of sarcosine in urine consists of a solid-phase microextraction (SPME) step followed by gas chromatography-triple quadrupole mass spectrometry analysis. We used a preliminary derivatization step with ethyl chloroformate/ethanol and the corresponding ester was then extracted by SPME in immersion mode. Several fibers were evaluated and the optimization of the parameters affecting the SPME process was carried out using an experimental design. The optimal values were 20 min extraction time, 10% NaCl, and 270°C using a divinylbenzene/Carboxen/polydimethylsiloxane fiber. The triple quadrupole analyzer acquired data in selected reaction monitoring mode, allowing us to obtain reconstructed chromatograms with well-defined chromatographic peaks. The accuracy and precision of this method were evaluated at concentrations of 70, 250, and 800 ng/ml and were found to be acceptable. Very satisfactory values (0.10 and 0.16 ng/ml, respectively) were also achieved for the limit of detection and the limit of quantification. The proposed protocol represents a rapid, simple, selective, and sensitive tool to quantify sarcosine in urine samples for prostate cancer diagnosis and for a screening test. [ABSTRACT FROM AUTHOR]

Abstract: Two unsupervised pattern recognition techniques such as stepwise linear discriminant analysis (SLDA) and Soft Independent Modeling of Class Analogy (SIMCA) were used to classify tomato samples in categories corresponding to the cultivation areas. The same approach was used for triple concentrated pastes for discrimination between two different Italian production areas. Accordingly, HS-SPME-GC-MS with 85μm carboxen/polydimethylsiloxane fiber was used for the determination of the volatile fraction in tomatoes and triple concentrate tomato pastes samples. Ethyl isobututanoate was used as internal standard for semiquantitative analysis and the concentration data (μg/kg) of 38 compounds for tomatoes and of 32 compounds for triple concentrates were used in following chemometric analysis. Sixteen and three variables were selected by forward stepwise LDA for tomatoes and pastes, respectively. SLDA and SIMCA models showed respectively 96% and 94% in term of prediction ability for tomatoes. The two supervised techniques provided 100% and 97% in prediction of the production areas of tomato pastes, respectively. [Copyright &y& Elsevier]

Abstract: Bergamot albedo, the white tissues between the skin and the pulp, is a polluting waste in the production of the renowned fragrance and is easily available by simple industrial processes. Brutieridin and melitidin are found in bergamot albedo and possess statin-like activity. Their anticholesterolaemic effect has been proved in vitro. Different procedures were exploited to assay the presence of brutieridin and melitidin and to evaluate their availability in water extracts. The best results in terms of simplicity and accessibility of the method were obtained with hot water at 65°C. Interestingly, tea beverages enriched with the two active principles have been obtained by simple addition of dried albedo into commercial tea bags. This is the first report on the availability of methodologies to extract active principles from citrus albedo wastes. [ABSTRACT FROM AUTHOR]

The history of the discovery of vitamins is the history of their deficiency disorders. Their discoverer was Casimir Funk, who is considered the 'father of vitamin therapy'. In his experimental research, Funk studied the interrelationships in the human body of those elements that Eijkman had demonstrated in animals, particularly in birds. In his experimental research, Funk identified the dietetic factors whose lack caused the 'deficiency disorders', as he called human beri-beri, scurvy, rickets and pellagra. In 1911, he designated these factors 'vitamins' ('vita' = life, and 'amine' = a nitrogenous substance essential for life); this name was accepted by the scientific community in 1912. Copyright © 2010 S. Karger AG, Basel [ABSTRACT FROM AUTHOR]