White Light-Photolysis for the Removal of Polycyclic Aromatic Hydrocarbons from Proximity Firefighting Protective Clothing.

The presence of polycyclic aromatic hydrocarbons (PAHs) on firefighters' personal protective equipment is a concern. One form of preventing from these compounds is to decontaminate proximity firefighting protective clothing (PFPC). Traditional decontamination methods do not promote total removal of pollutants and alter the properties of PFPC. The objective of this work was to evaluate the effectiveness of white light-photolysis (WLP), an advanced oxidation process (AOP), for removing PAHs from PFPC, while maintaining the integrity of the fabric fibers. Experiments were carried out, varying reaction time and concentration of H2O2. With WLP (without H2O2), it was possible to remove more than 73% of the PAHs tested from the outer layer of PFPC in 3 days. The WLP provided the greatest removal of PAHs, compared with the most common mechanical decontamination techniques (laundering and wet-soap brushing). The fibers' integrity after exposure to the white light was evaluated with infrared spectroscopy and scanning electron microscopy/energy dispersive X-ray spectrometry. In addition, a tearing strength test was performed. No remarkable fabric degradation was observed, indicating a possible, routine-compatible, simple, and inexpensive method of decontamination of PFPC, based on photolysis, which is effective in the degradation of PAHs and maintains the integrity of fabric fibers.

Analysis of Luminescent Gunshot Residue (LGSR) on Different Types of Fabrics.

The collection of gunshot residue on fabric can be an arduous task due to the microscopic size of particles (blind collection) and sheddability of some fabrics. The introduction of luminescent markers and consequent formation of luminescent gunshot residue (LGSR) can facilitate this analysis. In this study, different fabrics were analyzed in order to verify the persistence of the LGSR on them, the possibility of collecting and analyzing particles by video spectral comparator (VSC) and SEM/EDS. Also, different colored fabrics were used as targets in order to investigate influence of fabric color on LGSR visualization. Furthermore, the influence of the fabric type in the distribution of the LGSR deposited around the projectile´s hole entrance was evaluated. The fabric sheddability did not alter collection of the particles or analysis. It was possible to observe and collect LGSR on all tested fabrics, even after the fabric had been shaken, or in colored fabrics.

Interplay between the Mediterranean diet and C-reactive protein genetic polymorphisms towards inflammation in adolescents.

AIM: From a nutrigenetics perspective, we aim to investigate the moderating role of the Mediterranean diet and each of its subgroups in the association between C-reactive protein (CRP) gene polymorphisms and CRP blood concentration in adolescents. METHODS: In 562 adolescents (13-17 y) of the European HELENA study, data was available on circulating CRP levels as inflammatory biomarker, three CRP gene SNPs (rs3093068, rs1204, rs1130864), food intake determined by a self-administered computerized 24 h-dietary recall for 2 days, and body composition. A 9-point Mediterranean diet score and each food subgroup were tested as moderator via SNP*diet interaction. Analyzes were adjusted for age, sex, puberty, adiposity and socioeconomic status. RESULTS: The minor allele frequencies of rs3093068 and rs1130864 SNPs (GG and TT, respectively) were associated with higher CRP concentrations, while rs1205 (CT/TT) was associated with lower CRP concentrations. There were significant interactions between rs3093068 and Mediterranean diet (B = -0.1139, p = 0.011), or the fish food subgroup (B = -0.0090, p = 0.022), so that those with the highest genetic CRP risk underwent the highest CRP attenuation by a healthier diet. Although the effect of diet and SNP was substantial, the explained variance by interaction was only 1%. CONCLUSION: Greater adherence to the Mediterranean diet and particularly its fish component was associated with a lower CRP blood concentrations especially in those at highest genetic risk due to the rs3093068 SNP.

Relative validation of the adapted Mediterranean Diet Score for Adolescents by comparison with nutritional biomarkers and nutrient and food intakes: the Healthy Lifestyle in Europe by Nutrition in Adolescence (HELENA) study.

OBJECTIVE: To investigate whether adherence to the adapted Mediterranean Diet Score for Adolescents (MDS_A) and the adapted Mediterranean Diet Quality Index for Adolescents (KIDMED_A) is associated with better food/nutrient intakes and nutritional biomarkers. DESIGN: The Healthy Lifestyle in Europe by Nutrition in Adolescence (HELENA) study is a cross-sectional study aiming to obtain comparable data on a variety of nutritional and health-related parameters in European adolescents aged 12·5-17·5 years. SETTING: Nine European countries. PARTICIPANTS: European adolescents (n 2330) recruited to the HELENA study. Dietary intake was obtained with 24 h dietary recalls, an FFQ and a Food Choices and Preferences questionnaire. MDS_A was calculated as a categorical variable using cut-offs (MDS_A), as a continuous variable (zMDS_A) and with energy adjustments (zEnMDS_A). The KIDMED_A score was also calculated. RESULTS: Multilevel linear regression analysis showed positive associations for zMDS_A and KIDMED_A with serum levels of vitamin D, vitamin C, plasma folate, holo-transcobalamin, ß-carotene and n-3 fatty acids, while negative associations were observed with trans-fatty acid serum levels. For categorical indices, blood biomarkers showed few significant results. zMDS_A and KIDMED_A showed positive associations with vegetables and fruits intake, and negative associations with energy-dense and low-nutritious foods. zMDS_A and KIDMED_A were positively associated with all macronutrients, vitamins and minerals (all P < 0·0001), except with monosaccharides and PUFA for KIDMED_A and cholesterol for both indices (P < 0·05). CONCLUSIONS: zMDS_A and KIDMED_A have shown the strongest associations with the dietary indicators and biomarkers that have been associated with the Mediterranean diet before, and are therefore considered the most appropriate and valid Mediterranean diet scores for European adolescents.

Diet as a moderator in the association of sedentary behaviors with inflammatory biomarkers among adolescents in the HELENA study.

AIM: To assess if a healthy diet might attenuate the positive sedentary-inflammation relation, whereas an unhealthy diet may increase the effect of sedentary behaviors on inflammatory biomarkers. METHODS: In 618 adolescents (13-17 years) of the European HELENA study, data were available on body composition, a set of inflammation markers, and food intake assessed by a self-administered computerized 24 h dietary recall for 2 days. A 9-point Mediterranean diet score and an antioxidant-rich diet z-score were used as dietary indices and tested as moderators. A set of low-grade inflammatory characteristics was used as outcome: several cytokines in an inflammatory ratio (IL-6, IL-10, TNF-α, TGFß-1), C-reactive protein, three cell-adhesion molecules (sVCAM-1, sICAM-1, sE-selectin), three cardiovascular risk markers (GGT, ALT, homocysteine) and three immune cell types (white blood cells, lymphocytes, CD3). Sedentary behaviors were self-reported and analyzed as total screen time. Multiple linear regression analyses tested moderation by diet in the sedentary behaviors-inflammation association adjusted for age, sex, country, adiposity (sum of six skinfolds), parental education, and socio-economic status. RESULTS: Both diet scores, Mediterranean and antioxidant-rich diet, were significant protective moderators in the effect of sedentary behaviors on alanine-transaminase enzyme (P = 0.014; P = 0.027), and on the pro/anti-inflammatory cytokine ratio (P = 0.001; P = 0.004), but not on other inflammatory parameters. CONCLUSION: A higher adherence to the Mediterranean diet or an antioxidant-rich diet may attenuate the onset of oxidative stress signs associated by sedentary behaviors, whereas a poor diet seems to increase inflammation.

Diet as moderator in the association of adiposity with inflammatory biomarkers among adolescents in the HELENA study.

AIM: Our aim is to demonstrate that a healthy diet might reduce the relation between adiposity and inflammation, whereas an unhealthy diet may increase the effect of adiposity on inflammatory biomarkers. METHODS: In 618 adolescents (13-17 years) of the European HELENA study, data were available on body composition, a set of inflammation markers, and food intake determined by a self-administered computerized 24-h recall. A 9-point Mediterranean diet score and an antioxidant-rich diet score were used as dietary parameters and tested as moderator. Total body fat was represented by the sum of six skinfold thicknesses and central adiposity by waist circumference. A set of inflammation-related biomarkers was used as outcome: a pro/anti-inflammatory interleukins ratio, TGFß-1, C-reactive protein, TNF-α, 3 cell adhesion molecules, and 3 types of immune cells; gamma-glutamyltransferase (GGT) and homocysteine were used as cardiovascular disease risk biomarkers, and alanine transaminase (ALT) as liver dysfunction biomarker. Multiple linear regression analyses tested moderation by diet in the adiposity-inflammation association and were adjusted for age, sex, country, puberty, socioeconomic status. RESULTS: Both the Mediterranean and antioxidant-rich diet, and overall and central adiposity, were important in the moderation. Diet was a significant protective moderator in the effect of adiposity on the pro/anti-inflammatory interleukins ratio, TGFß-1, GGT, and ALT. CONCLUSION: In conclusion, in some cases, a diet rich in antioxidants and essential nutrients may attenuate the concentration of inflammatory biomarkers caused by adiposity, whereas a poor diet appears to contribute to the onset of early oxidative stress signs.

Associations between a Mediterranean diet pattern and inflammatory biomarkers in European adolescents.

AIM: To test whether the Mediterranean diet score and each food-subgroup is associated with inflammatory biomarkers in European adolescents. METHODS: In 464 adolescents (13-17 years) of the European HELENA study, data were available on body composition, inflammation markers, and food intake determined by two computerized 24-h recalls. The Mediterranean diet score and its food-subgroups (Vegetables, Fruits and Nuts, Pulses, Cereal and Roots, Monounsaturated/Saturated fat ratio, Dairy, Fish, Meat and Alcohol) were evaluated. A set of inflammation-related biomarkers was measured: IL-1, IL-2, IL-4, IL-5, IL-6, IL-10, TGFß-1, TNF-α, sVCAM-1, sICAM1, sE-selectin, white blood cells, lymphocytes, CD3, CRP, GGT, ALT, and homocysteine. Multivariate and multiple linear regression analyses were adjusted for age, sex, country, socioeconomic status, paternal and maternal education, adiposity, and smoking habits. RESULTS: The Mediterranean diet score was positively associated with CRP, and negatively with sVCAM-1. The subgroups showed the following positive/negative associations: Vegetables with IL-10(+), CRP(+), CD3(+), ALT(+), lymphocytes(+), sE-selectin(-); Fruits and Nuts with IL-4(-), TNF-alpha; Pulses with IL-5(+), IL-6(+), IL-2(-); Cereals and Roots with IL-6(-), IL-10(-); Monounsaturated/Saturated-fat ratio with IL-6(+), TGFß-1(+), sVCAM-1(+boys, -girls), homocysteine(-); Dairy with IL-1(+), IL-5(+), IL-6(+), IL-10(+), TGFß-1(+), homocysteine(-); Fish with homocysteine(-); Meat with IL-2(+), IL-10(+); Alcohol with CRP(+), lymphocytes(-). Sex differences were found. CONCLUSION: Some specific food-inflammation associations were found, suggesting that diet is to a certain extent already related to inflammation in adolescents and can be used in disease prevention. Also some counterintuitive results were found, which might be due to grouping very different foods into a single group, besides considering that the human body may respond differently depending on the interaction between diet, lifestyle, genetics, biochemical individuality, age and sex.

Inflammation and insulin resistance according to body composition in European adolescents: the HELENA study.

INTRODUCTION: Inflammation is related to insulin resistance in adults, especially on those individuals with high levels of body composition. OBJECTIVES: The aim of this study is to assess the relationship between a set of inflammatory biomarkers and insulin resistance by levels of body composition in a sample of European adolescents. MATERIAL AND METHODS: Nine hundred and sixty-two adolescents (442 boys and 520 girls) from nine European countries met the inclusion criteria of having measurements for the homeostasis model assessment (HOMA) and a set of inflammation-related biomarkers: C-reactive protein (CRP), tumor necrosis factor alpha (TNF-α), interleukin (IL-6), complement factors C3 and C4 and selected cell adhesion molecules. Body mass index (BMI), fat mass index (FMI) and waist circumference (WC) were categorized using tertiles. To assess the associations stratifying by body composition indexes, ANOVA and linear regression models were performed. RESULTS: Mean biomarkers' concentrations differed across BMI, FMI and WC tertiles (p < 0.05) by sex. In both sexes, insulin, HOMA, CRP, C3 and C4 were significantly different between categories (p < 0.001), always showing the highest mean concentration in the upper category of BMI, FMI and WC. The most consistent finding was an association between insulin resistance and C3 concentrations (p < 0.05), in the adolescents in the highest tertile of BMI, FMI and WC, except in the case of FMI in girls. CONCLUSION: Inflammatory and glucose metabolism markers differed by tertiles of body composition, being usually higher in the highest tertile. C3 complement factor was associated with insulin resistance in adolescents, especially those with high total and abdominal adiposity.

Inflammation and insulin resistance according to body composition in European adolescents: the HELENA study / Inflamación y resistencia a la insulina según composición corporal en adolescentes europeos: el estudio HELENA

Introduction: Inflammation is related to insulin resistance in adults, especially on those individuals with high levels of body composition. Objectives: The aim of this study is to assess the relationship between a set of inflammatory biomarkers and insulin resistance by levels of body composition in a sample of European adolescents. Material and methods: Nine hundred and sixty-two adolescents (442 boys and 520 girls) from nine European countries met the inclusion criteria of having measurements for the homeostasis model assessment (HOMA) and a set of inflammation-related biomarkers: C-reactive protein (CRP), tumor necrosis factor alpha (TNF-α), interleukin (IL-6), complement factors C3 and C4 and selected cell adhesion molecules. Body mass index (BMI), fat mass index (FMI) and waist circumference (WC) were categorized using tertiles. To assess the associations stratifying by body composition indexes, ANOVA and linear regression models were performed. Results: Mean biomarkers' concentrations differed across BMI, FMI and WC tertiles (p < 0.05) by sex. In both sexes, insulin, HOMA, CRP, C3 and C4 were significantly different between categories (p < 0.001), always showing the highest mean concentration in the upper category of BMI, FMI and WC. The most consistent finding was an association between insulin resistance and C3 concentrations (p < 0.05), in the adolescents in the highest tertile of BMI, FMI and WC, except in the case of FMI in girls. Conclusion: Inflammatory and glucose metabolism markers differed by tertiles of body composition, being usually higher in the highest tertile. C3 complement factor was associated with insulin resistance in adolescents, especially those with high total and abdominal adiposity (AU)

Introducción: la inflamación está relacionada con la resistencia a la insulina en adultos, especialmente en individuos con altos valores de composición corporal. Objetivos: valorar la relación entre diferentes marcadores inflamatorios y la resistencia a la insulina según valores de composición corporal en adolescentes europeos. Material y métodos: novecientos sesenta y dos adolescentes (442 chicos y 520 chicas) de nueve países europeos cumplían el criterio de inclusión de tener medidos la evaluación del modelo de homeostasis (HOMA) y diferentes marcadores inflamatorios: proteína C-reactiva (PCR), factor de necrosis tumoral alfa (TNF-α), interleukina (IL-6), factores de complemento C3 y C4 y moléculas de adhesión. El índice de masa corporal (IMC), el índice de masa grasa (IMG) y la circunferencia de cintura (CC) se categorizaron en tertiles. Para valorar las asociaciones por índices de composición corporal se realizó ANOVA y regresión. Resultados: las concentraciones de los marcadores diferían entre los tertiles de IMC, IMG y CC (p < 0,05), por sexo. En ambos sexos, insulina, HOMA, PCR, C3 y C4 fueron significativamente diferentes entre categorías (p < 0,001), presentando la mayor concentración en la categoría superior de IMC, IMG y CC. El resultado más consistente para los adolescentes del tertil superior de IMC, IMG y CC fue la asociación entre resistencia a la insulina y concentraciones de C3 (p < 0,05), excepto para IMG en chicas. Conclusión: los marcadores del metabolismo inflamatorio y de la glucosa diferían según tertiles de composición corporal, siendo mayores en el tertil superior. El C3 se asoció con resistencia a la insulina en adolescentes, especialmente en aquellos con adiposidad total y abdominal (AU)

Association between dietary inflammatory index and inflammatory markers in the HELENA study.

BACKGROUND: Previous research has shown that diet is associated with low-grade systemic inflammation among adults. However, no study has yet been conducted to explore the association between inflammatory potential of diet and low-grade systemic inflammation among adolescents whose dietary behavior may be different from adults. METHODS AND RESULTS: We examine the predictive ability of 24-h recall-derived dietary inflammatory index (DII) scores on inflammation among 532 European adolescents in the HELENA cross-sectional study. The DII is a literature-derived dietary index developed to predict inflammation. The DII was calculated per 1000 calories and was tested against C-reactive protein, ILs-1,2,4,10, TNF-α, ICAM, vascular cell adhesion molecule (VCAM), and IFN-γ. All inflammatory markers had nonnormal distributions and therefore were log transformed. Analyses were performed using multivariable linear regression, adjusting for age, sex, city, BMI, smoking, and physical activity. Pro-inflammatory diet (higher DII scores) was associated with increased levels of various inflammatory markers: TNF-α, IL-1, 2, IFN-γ,  and vascular cell adhesion molecule (bDIIt3vs1 = 0.13, 95% CI: 0.001, 0.25; 0.13, 95% CI 0.001, 0.25; 0.40, 95% CI: 0.03, 0.77; 0.53, 95% CI: 0.05, 1.01; 0.07, 95% CI: 0.01, 0.13, respectively). CONCLUSION: These results reinforce the fact that diet, as a whole, plays an important role in modifying inflammation in adolescents.

Application of the Metal-Organic Framework [Eu(BTC)] as a Luminescent Marker for Gunshot Residues: A Synthesis, Characterization, and Toxicity Study.

The 3D metal-organic framework (MOF) [Eu(BTC)] (where BTC = trimesic acid) was synthesized in 20 min by a microwave-assisted hydrothermal method with a yield of 89%. A structural and spectroscopic study, performed by X-ray diffraction, thermogravimetry, and photoluminescence spectroscopy, showed that this framework has high crystallinity, thermal stability, and luminescence. This MOF had a red-orange luminescence when excited with ultraviolet (UV) radiation (λ = 254 nm) and a high potential for use as a luminescent marker for gunshot residues (GSR). When added to 9 mm nontoxic ammunition, it greatly improved quality of the crime scene investigation, allowing for direct visualization of the luminescent GSR on the shooter's hand and firearm and at the firing range using only a portable UV lamp. The marked luminescent GSR was easily collected and characterized by nondestructive techniques, including with a Video Spectral Comparator and scanning electron microscopy/energy-dispersive spectroscopy, wherein the presence of Eu3+ ions was confirmed. Furthermore, the oral acute toxicity of this MOF was assessed in adult female Wistar rats using the Organisation for Economic Cooperation and Development 423 guidelines. This study classified the MOF [Eu(BTC)] in a less toxic Globally Harmonized System category (category 5), with a LD50 (lethal dose) of 5000 mg/kg, ensuring a wide security range for its application.

Ionically tagged iron complex-catalyzed epoxidation of olefins in imidazolium-based ionic liquids.

A new ionophilic ligand and a new ionically tagged imidazolium-based iron(III) complex were synthesized and applied in the air oxidation (also hydrogen peroxide) of alkenes in imidazolium-based ionic liquids. At least ten recycling reactions were performed. The epoxidized olefin was obtained in very good yields of 84-91 %. Some important mechanistic insights are also provided based on electrospray ionization quadrupole-time of flight mass spectrometry for the oxidation reaction. These results indicate that oxidations can take place by two different pathways, depending on the reaction condition: a radical or a concerted mechanism. These results contribute towards a better understanding of iron-catalyzed oxidation mechanisms.