Experimental validation of a geographical information systems-based procedure for predicting pesticide exposure in surface water

A GIS-based procedure for predicting pesticide exposure in surface waters has been applied on a pilot river basin characterized by intensive agricultural activity. The predictive approach has been validated through experimental monitoring, performed by collecting manual and automatic water samples during the productive season. Five active ingredients (terbuthylazine, metolachlor, alachlor, linuron, fenitrothion) were selected for analysis to validate the predictive approach. Comparison between predicted and experimental values showed good agreement for terbuthylazine and metolachlor (used in large volumes within the basin), demonstrating the reliability of the approach. However, some anomalous results were obtained for some of the other chemicals, which serve to highlight the difficulties in getting reliable input data, in particular on application patterns (rate and time). Furthermore, the value of mapping pesticide exposure on the medium-large scale is described, and the limitations of the reported predictive approach are discussed.     

Lipidomic Approaches to Study HDL Metabolism in Patients with Central Obesity Diagnosed with Metabolic Syndrome

The metabolic syndrome (MetS) is a cluster of cardiovascular risk factors characterised by central obesity, atherogenic dyslipidaemia, and changes in the circulating lipidome; the underlying mechanisms that lead to this lipid remodelling have only been partially elucidated. This study used an integrated “omics” approach (untargeted whole serum lipidomics, targeted proteomics, and lipoprotein lipidomics) to study lipoprotein remodelling and HDL composition in subjects with central obesity diagnosed with MetS (vs. controls). Compared with healthy subjects, MetS patients showed higher free fatty acids, diglycerides, phosphatidylcholines, and triglycerides, particularly those enriched in products of de novo lipogenesis. On the other hand, the “lysophosphatidylcholines to phosphatidylcholines” and “cholesteryl ester to free cholesterol” ratios were reduced, pointing to a lower activity of lecithin cholesterol acyltransferase (LCAT) in MetS; LCAT activity (directly measured and predicted by lipidomic ratios) was positively correlated with high-density lipoprotein cholesterol (HDL-C) and negatively correlated with body mass index (BMI) and insulin resistance. Moreover, many phosphatidylcholines and sphingomyelins were significantly lower in the HDL of MetS patients and strongly correlated with BMI and clinical metabolic parameters. These results suggest that MetS is associated with an impairment of phospholipid metabolism in HDL, partially led by LCAT, and associated with obesity and underlying insulin resistance. This study proposes a candidate strategy to use integrated “omics” approaches to gain mechanistic insights into lipoprotein remodelling, thus deepening the knowledge regarding the molecular basis of the association between MetS and atherosclerosis.     

Effects of Different Types of Chronic Training on Bioenergetic Profile and Reactive Oxygen Species Production in LHCN-M2 Human Myoblast Cells

Human skeletal muscle contains three different types of fibers, each with a different metabolism. Exercise differently contributes to differentiation and metabolism in human myoblast cells. The aims of the present study were to investigate the effects of different types of chronic training on the human LHCN-M2 myoblast cell bioenergetic profile during differentiation in real time and on the ROS overproduction consequent to H₂O₂ injury. We demonstrated that exercise differently affects the myoblast bioenergetics: aerobic exercise induced the most efficient glycolytic and oxidative capacity and proton leak reduction compared to untrained or anaerobic trained sera-treated cells. Similarly, ROS overproduction after H₂O₂ stress was lower in cells treated with differently trained sera compared to untrained sera, indicating a cytoprotective effect of training on the reduction of oxidative stress, and thus the promotion of longevity. In conclusion, for the first time, this study has provided knowledge regarding the modifications induced by different types of chronic training on human myoblast cell bioenergetics during the differentiation process in real time, and on ROS overproduction due to stress, with positive implications in terms of longevity.     

Chiral Discrimination Mechanisms by Silylated-Acetylated Cyclodextrins: Superficial Interactions vs. Inclusion

Cyclodextrin derivatives constitute a powerful class of auxiliary agents for the discrimination of apolar chiral substrates. Both host–guest inclusion phenomena and interactions with the derivatizing groups located on the surface of the macrocycle could drive the enantiodiscrimination; thus, it is important to understand the role that these processes play in the rational design of new chiral selectors. The purpose of this study is to compare via nuclear magnetic resonance (NMR) spectroscopy the efficiency of silylated-acetylated α-, β-, and γ-cyclodextrins in the chiral discrimination of 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane (compound B) and methyl 2-chloropropionate (MCP). NMR DOSY (Diffusion Ordered SpectroscopY) experiments were conducted for the determination of the bound molar fractions and the association constants, whereas ROESY (Rotating-frame Overhauser Enhancement SpectroscopY) measurements provided information on the hosts’ conformation and on the interaction phenomena with the guests. Compound B, endowed with fluorinated moieties, is not deeply included due to attractive Si-F interactions occurring at the external surface of the cyclodextrins. Therefore, a low selectivity toward the size of cyclodextrin cavity is found. By contrast, enantiodiscrimination of MCP relies on the optimal fitting between the size of the guest and that of the cyclodextrin cavity.     

The ATP-binding site of protein kinase CK2 holds a positive electrostatic area and conserved water molecules

CK2 is a highly pleiotropic Ser/Thr protein kinase that is able to promote cell survival and enhance the tumour phenotype under specific circumstances. We have determined the crystal structure of three new complexes with tetrabromobenzimidazole derivatives that display K(i) values between 0.15 and 0.30 microM. A comparative analysis of these data with those of four other inhibitors of the same family revealed the presence of some highly conserved water molecules in the ATP-binding site. These waters reside near Lys68, in an area with a positive electrostatic potential that is able to attract and orient negatively charged ligands. The presence of this positive region and two unique bulky residues that are typical of CK2, Ile66 and Ile174, play a critical role in determining the ligand orientation and binding selectivity.     

Anti-fingerprints fluorinated coating for anodized titanium avoiding color alteration

In this study amorphous fluorinated coatings applied to anodized titanium surface have been investigated. A copolymer between tetrafluoroethylene and perfluoro-4-trifluoromethoxy-1,3-dioxole (AD60) and two perfluoropolyether containing ammonium phosphate (F10) or triethoxysilane (S10) functionalities have been tested. To estimate the color alteration of the anodized titanium surfaces due to the application of the coatings, spectrophotometric analyses have been made. Water and n-dodecane contact angles as well as apparent surface energy have been evaluated. Ellipsometry and atomic force microscopy data have been used to measure the thickness of the fluorinated coatings. A tailored mechanical preliminary test has also been explored to evaluate the adhesion of the coatings on the anodized titanium surface. The resistance to surface soiling with castor oil was also preliminarily investigated. The fluorinated coating tested on anodized titanium showed a low apparent surface energy and high chromatic aspect conservation, this is particularly evident for the titanium anodized coated with triethoxysilane functionalities fluoropolymers S10.     

Deactivation of a Ni-Based Reforming Catalyst During the Upgrading of the Producer Gas, from Simulated to Real Conditions

The deactivation of a nickel reforming catalyst during the upgrading of the producer gas obtained by gasification of lignocellulosic biomass was studied. The research involved several steps: the selective deactivation of the catalyst in a laboratory scale; the streaming of the catalyst with the producer gas of a downdraft and an oxygen/steam circulating fluidized bed (CFB) gasifier; and tests in a reformer placed in a slipstream of the CFB gasifier. The information obtained allowed to elucidate the catalyst deactivation mechanisms taking place during the reforming of the producer gas: physical deactivation by deposition of fine ashes, aerosol particulate or carbon; poisoning by H₂S and HCl present in the gas phase and thermal sintering because of the high operation temperatures required to avoid the chemical deactivation. These physical and chemical effects depended on the composition of the biomass fuel.     

A triple spin-labeling strategy coupled with DEER analysis to detect DNA modifications and enzymatic repair

In a spin: Spin-labeled oligonucleotides produced by click chemistry can be studied by EPR, by using a DEER sequence. This was used to test a complex triple-labeling strategy with damaged DNA. Extensive and accurate analysis of DNA structure and enzymatic repair processes were performed after digestion by EndoIV. Modified DNA structures and DNA-protein interactions can now be readily studied.