Absolute configuration sensing of chiral aryl-and aryloxy-propionic acids by biphenyl chiroptical probes

The absolute configuration of chiral 2-aryl and 2-aryloxy propionic acids, which are among the most common chiral environmental pollutants, has been readily and reliably established by either electronic circular dichroism spectroscopy or optical rotation measurements employing suitably designed 4,4′-disubstituted biphenyl probes. In fact, the 4,4′-biphenyl substitution gives rise to a red shift of the diagnostic electronic circular dichroism signal of the biphenyl A band employed for the configuration assignment, removing its overlap with other interfering dichroic bands and allowing its clear sign identification. The largest A band red shift, and thus the most reliable results, are obtained by employing as a probe the 4,4′-dinitro substituted biphenylazepine 3c. The method was applied to the absolute configuration assignment of 2-arylpropionic acids ibuprofen (1a), naproxen (1b), ketoprofen (1c) and flurbiprofen (1d), as well as to the 2-aryloxypropionic acids 2-phenoxypropionic acid (2a) and 2-naphthoxypropionic acid (2b). This approach, allowing us to reveal the sample’s absolute configuration by simple optical rotation measurements, is potentially applicable to online analyses of both the enantiomeric composition and absolute configuration of these chiral pollutants

Effect of hazelnut on serum lipid profile and fatty acid composition of erythrocyte phospholipids in children and adolescents with primary hyperlipidemia : a randomized controlled trial

Background & aim: Regular intake of nuts improves lipid profile and thus reduces the cardiovascular (CV) risk associated with hyperlipidemia. The aim of the study was to investigate the effect of a dietary intervention with hazelnuts (HZNs, 15-30 g/day, depending on patient weight) on serum lipid profile, anthropometric parameters and fatty acids (FAs) composition of erythrocyte phospholipids in children and adolescents with primary hyperlipidemia. Methods: Eight-week randomized, single blind, controlled, three-arm, parallel-group study. Sixty-six subjects were enrolled and randomized in 3 groups receiving: 1) hazelnuts with skin (HZN+S); 2) hazelnuts without skin (HZN-S); 3) dietary advices for hyperlipidemia only (controls). Before and after intervention, clinical parameters were measured and blood samples were collected for the evaluation of serum lipid levels and phospholipid FA composition of erythrocytes. Results: Two-way ANOVA showed a significant effect of time on serum low-density lipoprotein cholesterol (LDL-C), high-density lipoprotein cholesterol (HDL-C)/LDL-C ratio and non-HDL-C (p < 0.001), but not of treatment and time x treatment interaction. In particular, HZN+S and HZN-S significantly reduced the concentrations of LDL-C and increased HDL-C/LDL-C ratio. HZNs also had a favorable impact on FAs composition of erythrocyte phospholipids, as demonstrated by time x treatment interaction, with a significant increase of monounsaturated fatty acids (MUFAs) (p = 0.008) and MUFAs/saturated fatty acids (SFAs) ratio (p = 0.002) with respect to the control group. Conclusions: For the first time, we documented a positive effect of HZN consumption on lipid profile and FA composition of erythrocyte phospholipids in children with primary hyperlipidemia. Further studies are encouraged to better define HZN impact on the markers of CV risk in this population

Three-dimensional structure of human cyclooxygenase (hCOX)-1

The beneficial effects of Cyclooxygenases (COX) inhibitors on human health have been known for thousands of years. Nevertheless, COXs, particularly COX-1, have been linked to a plethora of human diseases such as cancer, heart failure, neurological and neurodegenerative diseases only recently. COXs catalyze the first step in the biosynthesis of prostaglandins (PGs) and are among the most important mediators of inflammation. All published structural work on COX-1 deals with the ovine isoenzyme, which is easier to produce in milligram-quantities than the human enzyme and crystallizes readily. Here, we report the long-sought structure of the human cyclooxygenase-1 (hCOX-1) that we refined to an R/Rfree of 20.82/26.37, at 3.36 Å resolution. hCOX-1 structure provides a detailed picture of the enzyme active site and the residues crucial for inhibitor/substrate binding and catalytic activity. We compared hCOX-1 crystal structure with the ovine COX-1 and human COX-2 structures by using metrics based on Cartesian coordinates, backbone dihedral angles, and solvent accessibility coupled with multivariate methods. Differences and similarities among structures are discussed, with emphasis on the motifs responsible for the diversification of the various enzymes (primary structure, stability, catalytic activity, and specificity). The structure of hCOX-1 represents an essential step towards the development of new and more selective COX-1 inhibitors of enhanced therapeutic potential

Prescription Opioid Use among Pregnant Women Enrolled in Rhode Island Medicaid

Objective: Our objective was to identify the patterns of opioid use among pregnant women enrolled in RI Medicaid. Methods: This study used linked RI Medicaid and RI Birth Certificate data from 01/01/2006 to 12/31/2016. We examined temporal trends of prescription opioid dispensings and identified risk factors associated with opioids use during pregnancy. Results: Among 25,500 RI Medicaid enrolled pregnant women who delivered a live baby from 2008 to 2016, 1,914 (7.5%) received at least one prescription for an opioid medication during pregnancy, 810 (3.2%) were during the first trimester, 633 (2.5%) during the second trimester, and 866 (3.4%) during the third trimester. Of these, 213 (0.8%) women received 3 or more opioids during pregnancy. The prevalence of prescription opioids dispensed in pregnant women increased from 4.9% in 2008 to 9.6% in 2015 (β SD: 0.66 0.28, P=0.05). Conclusions: Prescription opioid use during pregnancy has increased among women enrolled in RI Medicaid

Groundwater flow process in the active volcanic system of Ischia Island (Italy)

The volcanic system of Ischia is characterized by an intense hydrothermal activity, documented since the early 16th century by the study of Iasolino (1588), which represents the first systematic analysis of the thermal springs of the island for therapeutic purposes. Later studies partially contributed to the enhancement of knowledge on the volcanic, hydrogeological and hydrothermal features of the island, highlighting the strong interaction between hydrothermal flowpaths and volcano- tectonic processes. The reconstruction of the interplay between hydrothermal and magmatic system becomes, therefore, a fundamental element for territorial planning, not only in terms of management of the huge water and geothermal resource, but also in a perspective of prevention and mitigation of volcanic risk. Thermal springs, fumaroles and mud deposits give beginning clues about deep hydrothermal conditions. Till now at Ischia, the local geochemical characterization of fluids and groundwater has been used for the definition of the origin and structure of the hydrothermal system as a whole, as the hydrogeological information is incomplete. However, volcanic hydrothermal systems, such as that characterizes the island of Ischia, are particularly difficult to analyze and outline, as the groundwater resources are the result of a complex and dynamic mixing among meteoric water, sea water and deep fluids. In such cases, the need for an interdisciplinary approach is evident, involving knowledge and research methods ranging from geology to volcanology, geophysics, geochemistry and hydrogeology. With particular reference to the functional and structural representation of the geothermal system of the Ischia island and the resulting correlations with the volcano-tectonic processes, the examination of previous information highlights the need to update and improve the knowledge on groundwater hydrodynamics and mineralization processes. Therefore, the present study aims at a strongly interdisciplinary action that, starting from the design and implementation of a database on the existing geological/volcanological and hydrogeological information, will contribute to highlight the critical issues, define an operating scheme of the hydro-geo-thermal system of the island of Ischia, and upgrade its hydrogeological, geochemical and volcanic monitoring system. The preliminary results improved the definition of the hydrogeological complexes and advanced knowledge of the groundwater flow conditions

Groundwater flow characterization and reconstruction of the hydrothermal system of Ischia as a tool for volcanic risk mitigation

The volcanic system of Ischia is characterized by an intense hydrothermal activity, documented since the early 16th century by the study of Iasolino [1588], which represents the first systematic analysis of the thermal springs of the island for therapeutic purposes. Later studies partially contributed to the enhancement of knowledge on the volcanic, hydrogeological and hydrothermal features of the island, highlighting the strong interaction between hydrothermal flowpaths and volcanotectonic processes. The reconstruction of the hydrothermal system becomes, therefore, a fundamental element for territorial planning, not only in terms of management of the huge water and geothermal resource, but also and above all in a perspective of prevention and mitigation of volcanic risk. Thermal springs, fumaroles and clay deposits due to the hydrothermal alteration of volcanic products testifies for the existence of an active deep hydrothermal system. However at Ischia the geochemical characterization of fluids and groundwater, performed through sampling and analysis of a discrete number of scattered springs, wells and fumaroles, has been used for the definition of the origin and structure of hydrothermal systems as a whole, as the hydrogeological information is incomplete. Moreover, volcanic hydrothermal systems, such as that characterizes the island of Ischia, are particularly difficult to analyze and outline, as the groundwater resources are the result of an articulated and dynamic interaction among meteoric water, sea water and fluids of deep origin. In such cases, the need for an interdisciplinary approach is evident, involving knowledge and research methods ranging from geology to volcanology, geophysics, geochemistry, mineralogy and hydrogeology. With particular reference to the functional and structural representation of the geothermal system of the island of Ischia and the resulting correlations with the volcanotectonic processes, the examination of previous information highlights the need to update and improve the knowledge on groundwater hydrodynamics and mineralization processes. Therefore, the present work represents a strong interdisciplinary action that, starting from the design and implementation of a database on the existing geological/volcanological and hydrogeological information, contributes to highlight the critical issues, define an operating scheme of the hydrogeothermal system of the island of Ischia, and upgrade its hydrogeological, geochemical and volcanic monitoring system, in order to contribute to the mitigation of volcanic and related risks. The knowledge of groundwater dynamics and pathways, in fact, is of fundamental importance for understanding the water/magma interaction processes in case of realimentation of the shallow magmatic system, and the assessment of the possibility of phreatic explosions occurrence. Moreover, the knowledge of the thermal fluids’ circulation and the related rock alteration processes is of paramount importance in the definition of the mechanic characteristics of rock masses and their proneness to failure

Spatial and temporal variability of the dimethylsulfide to chlorophyll ratio in the surface ocean: an assessment based on phytoplankton group dominance determined from space

Dimethylsulfoniopropionate (DMSP) is produced in surface seawater by phytoplankton. Phytoplankton culture experiments have shown that nanoeucaryotes (NANO) display much higher mean DMSP-to-Carbon or DMSP-to-Chlorophyll (Chl) ratios than Prochlorococcus (PRO), Synechococcus (SYN) or diatoms (DIAT). Moreover, the DMSP-lyase activity of algae which cleaves DMSP into dimethylsulfide (DMS) is even more group specific than DMSP itself. Ship-based observations have shown at limited spatial scales, that sea surface DMS-to-Chl ratios (DMS:Chl) are dependent on the composition of phytoplankton groups. Here we use satellite remote sensing of Chl (from SeaWiFS) and of Phytoplankton Group Dominance (PGD from PHYSAT) with ship-based sea surface DMS concentrations (8 cruises in total) to assess this dependence on an unprecedented spatial scale. PHYSAT provides PGD (either NANO, PRO, SYN, DIAT, Phaeocystis (PHAEO) or coccolithophores (COC)) in each satellite pixel (1/4° horizontal resolution). While there are identification errors in the PHYSAT method, it is important to note that these errors are lowest for NANO PGD which we typify by high DMSP:Chl. In summer, in the Indian sector of the Southern Ocean, we find that mean DMS:Chl associated with NANO + PHAEO and PRO + SYN + DIAT are 13.6±8.4 mmol g−1 (n=34) and 7.3±4.8 mmol g−1 (n=24), respectively. That is a statistically significant difference (P<0.001) that is consistent with NANO and PHAEO being relatively high DMSP producers. However, in the western North Atlantic between 40° N and 60° N, we find no significant difference between the same PGD. This is most likely because coccolithophores account for the non-dominant part of the summer phytoplankton assemblages. Meridional distributions at 22° W in the Atlantic, and 95° W and 110° W in the Pacific, both show a marked drop in DMS:Chl near the equator, down to few mmol g−1, yet the basins exhibit different PGD (NANO in the Atlantic, PRO and SYN in the Pacific). In tropical and subtropical Atlantic and Pacific waters away from the equatorial and coastal upwelling, mean DMS:Chl associated with high and low DMSP producers are statistically significantly different, but the difference is opposite of that expected from culture experiments. Hence, in a majority of cases PGD is not of primary importance in controlling DMS:Chl variations. We therefore conclude that water-leaving radiance spectra obtained simultaneously from ocean color sensor measurements of Chl concentrations and dominant phytoplankton groups can not be used to predict global fields of DMS

Carbonyl sulfide : comparing a mechanistic representation of the vegetation uptake in a land surface model and the leaf relative uptake approach

Land surface modellers need measurable proxies to constrain the quantity of carbon dioxide (CO2) assimilated by continental plants through photosynthesis, known as gross primary production (GPP). Carbonyl sulfide (COS), which is taken up by leaves through their stomates and then hydrolysed by photosynthetic enzymes, is a candidate GPP proxy. A former study with the ORCHIDEE land surface model used a fixed ratio of COS uptake to CO2 uptake normalised to respective ambient concentrations for each vegetation type (leaf relative uptake, LRU) to compute vegetation COS fluxes from GPP. The LRU approach is known to have limited accuracy since the LRU ratio changes with variables such as photosynthetically active radiation (PAR): while CO2 uptake slows under low light, COS uptake is not light limited. However, the LRU approach has been popular for COS-GPP proxy studies because of its ease of application and apparent low contribution to uncertainty for regional-scale applications. In this study we refined the COS-GPP relationship and implemented in ORCHIDEE a mechanistic model that describes COS uptake by continental vegetation. We compared the simulated COS fluxes against measured hourly COS fluxes at two sites and studied the model behaviour and links with environmental drivers. We performed simulations at a global scale, and we estimated the global COS uptake by vegetation to be -756 Gg S yr(-1) , in the middle range of former studies (-490 to -1335 Gg S yr(-1)). Based on monthly mean fluxes simulated by the mechanistic approach in ORCHIDEE, we derived new LRU values for the different vegetation types, ranging between 0.92 and 1.72, close to recently published averages for observed values of 1.21 for C-4 and 1.68 for C-3 plants. We transported the COS using the monthly vegetation COS fluxes derived from both the mechanistic and the LRU approaches, and we evaluated the simulated COS concentrations at NOAA sites. Although the mechanistic approach was more appropriate when comparing to high-temporal-resolution COS flux measurements, both approaches gave similar results when transporting with monthly COS fluxes and evaluating COS concentrations at stations. In our study, uncertainties between these two approaches are of secondary importance compared to the uncertainties in the COS global budget, which are currently a limiting factor to the potential of COS concentrations to constrain GPP simulated by land surface models on the global scale.Peer reviewe