Search

A gas-phase nitrogen-nitrogen noncovalent interaction has been unveiled in the nitroethane-trimethylamine complex in an environment free from solvent and matrix effects using rotational spectroscopy in supersonic expansion. Different quantum chemical models (NOCV/CD and NBO) agree in indicating that this interaction largely prevails over the C-H⋅⋅⋅O and C-H⋅⋅⋅N hydrogen bonds. Furthermore, a SAPT analysis shows that electrostatic and dispersion interactions play a comparable role in stabilizing the complex. The conformational landscape exploration and stationary points characterization have been performed using state-of-the-art quantum-chemical computations providing significant insights on structure determination., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objectives: to explore clinicians vision on hospital discharge records in order to identify useful elements to foster a more accurate compiling., Design: qualitative research with phenomenological approach., Setting and Participants: participants were selected through purposive sampling among clinicians of two hospitals located in Sardinia; the sample included 76 people (32 medical directors and 44 doctors in training)., Main Outcome Measures: identified codes for themes under investigation: vision of accurate compiling, difficulties, and proposals., Results: collected data highlighted two prevailing visions, respectively focused on the importance of an accurate compiling and on the burden of such activity. The accurate compiling is hindered by the lack of motivation and training, by the limits of the registration system and the information technology, by the distortions induced by the prominent role of the hospital discharge records in the evaluation processes. Training, timely updating of the information system accompanied by a proper cross-cultural validation process, improvement of the computer system, and activation of support services could promote more accurate compiling., Conclusions: the implementation of services, unconnected with evaluation and control processes, dedicated to training and support in the compiling of the hospital discharge records and in the conduction of related epidemiological studies would facilitate the compliance to the compilation. Such services will make tangible the benefits obtainable from this registration system, increasing skills, motivation, ownership, and facilitating greater accuracy in compiling.

Context: C-cyanomethanimine (HNCHCN), existing in the two Z and E isomeric forms, is a key prebiotic molecule, but, so far, only the E isomer has been detected toward the massive star-forming region. Sagittarius B2(N) using transitions in the radio wavelength domain., Aims: With the aim of detecting HNCHCN in Sun-like-star forming regions, the laboratory investigation of its rotational spectrum has been extended to the millimeter-/submillimeter-wave (mm-/submm-) spectral window in which several unbiased spectral surveys have been already carried out., Methods: High-resolution laboratory measurements of the rotational spectrum of C-cyanomethanimine were carried out in the 100-420 GHz range using a frequency-modulation absorption spectrometer. We then searched for the C-cyanomethanimine spectral features in the mm-wave range using the high-sensitivity and unbiased spectral surveys obtained with the IRAM 30-m antenna in the ASAI context, the earliest stages of star formation from starless to evolved Class I objects being sampled., Results: For both the Z and E isomers, the spectroscopic work has led to an improved and extended knowledge of the spectroscopic parameters, thus providing accurate predictions of the rotational signatures up to ~700 GHz. So far, no C-cyanomethanimine emission has been detected toward the ASAI targets, and upper limits of the column density of ~ 10 11 -10 12 cm -2 could only be derived. Consequently, the C-cyanomethanimine abundances have to be less than a few 10 -10 for starless and hot-corinos. A less stringent constraint, ≤ 10 -9 , is obtained for shocks sites., Conclusions: The combination of the upper limits of the abundances of C-cyanomethanimine together with accurate laboratory frequencies up to ~ 700 GHz poses the basis for future higher sensitivity searches around Sun-like-star forming regions. For compact (typically less than 1″) and chemically enriched sources such as hot-corinos, the use of interferometers as NOEMA and ALMA in their extended configurations are clearly needed.

The Virtual Multifrequency Spectrometer (VMS) is a tool that aims at integrating a wide range of computational and experimental spectroscopic techniques with the final goal of disclosing the static and dynamic physical-chemical properties "hidden" in molecular spectra. VMS is composed of two parts, namely, VMS-Comp, which provides access to the latest developments in the field of computational spectroscopy, and VMS-Draw, which provides a powerful graphical user interface (GUI) for an intuitive interpretation of theoretical outcomes and a direct comparison to experiment. In the present work, we introduce VMS-ROT, a new module of VMS that has been specifically designed to deal with rotational spectroscopy. This module offers an integrated environment for the analysis of rotational spectra: from the assignment of spectral transitions to the refinement of spectroscopic parameters and the simulation of the spectrum. While bridging theoretical and experimental rotational spectroscopy, VMS-ROT is strongly integrated with quantum-chemical calculations, and it is composed of four independent, yet interacting units: (1) the computational engine for the calculation of the spectroscopic parameters that are employed as a starting point for guiding experiments and for the spectral interpretation, (2) the fitting-prediction engine for the refinement of the molecular parameters on the basis of the assigned transitions and the prediction of the rotational spectrum of the target molecule, (3) the GUI module that offers a powerful set of tools for a vis-à-vis comparison between experimental and simulated spectra, and (4) the new assignment tool for the assignment of experimental transitions in terms of quantum numbers upon comparison with the simulated ones. The implementation and the main features of VMS-ROT are presented, and the software is validated by means of selected test cases ranging from isolated molecules of different sizes to molecular complexes. VMS-ROT therefore offers an integrated environment for the analysis of the rotational spectra, with the innovative perspective of an intimate connection to quantum-chemical calculations that can be exploited at different levels of refinement, as an invaluable support and complement for experimental studies.

Introduction: Healthcare associated infections (HAIs) are a cause of high morbidity, disability and reduced quality of life, as well as mortality and rising costs for health systems. Preventing the HAI risk by planning and implementing effective preventive strategies is important to safeguard patient health., Methods: The study aimed to evaluate the presence of procedures and protocols for infection control, to assess the adhesion to the different aspects of hand hygiene (HH) and hand washing technique by healthcare workers in six ICUs. A perspective observational study was conducted in six ICUs. In each ICU, the adherence by health care workers to both hand hygiene practices and standard precautions was assessed, as well as the presence of procedures and written protocols., Results: The findings showed that in all the involved ICUs, 73 of 142 required protocols and procedures were available. Specifically, 59 of 79 were available for general measure of risk control, 12 of 15 for hand hygiene, and 24 of 48 for standard precautions and isolation measures. Also, the results showed highly variable levels of adherence to the best hygiene practices in all the ICUs involved in the study, with compliance rates ranging from 3% to 100%, and 73 of 142 required protocols were available at the study time., Conclusions: Overall, the involved ICUs showed low levels of adherence to best hygiene practices. This suggests the need to implement immediate strategies for infection control in the ICUs. A multidisciplinary intervention could be effective in preventing and control the HAI risk.score was reached only by the third year students with regard to the proper HH. The level of knowledge about HAI was inadequate.A periodically check of nursing students' knowledge would be advisable in order to fill any gaps, improve training, reduce HAI and increase prevention measures compliance.

The 1:1 complex of tert-butyl alcohol with difluoromethane has been characterized by means of a joint experimental-computational investigation. Its rotational spectrum has been recorded by using a pulsed-jet Fourier-Transform microwave spectrometer. The experimental work has been guided and supported by accurate quantum-chemical calculations. In particular, the computed potential energy landscape pointed out the formation of three stable isomers. However, the very low interconversion barriers explain why only one isomer, showing one O-H···F and two C-H···O weak hydrogen bonds, has been experimentally characterized. The effect of the H → tert -butyl- group substitution has been analyzed from the comparison to the difluoromethane-water adduct.

The 1:1 complex of ammonia with pyridine is characterized by using state-of-the-art quantum-chemical computations combined with pulsed-jet Fourier-transform microwave spectroscopy. The computed potential energy landscape indicates the formation of a stable σ-type complex, which is confirmed experimentally: analysis of the rotational spectrum shows the presence of only one 1:1 pyridine-ammonia adduct. Each rotational transition is split into several components owing to the internal rotation of NH 3 around its C 3 axis and to the hyperfine structure of both 14 N quadrupolar nuclei, thus providing unequivocal proof that the two molecules form a σ-type complex involving both a N-H⋅⋅⋅N and a C-H⋅⋅⋅N hydrogen bond. The dissociation energy (BSSE- and ZPE-corrected) is estimated to be 11.5 kJ mol -1 . This work represents the first application of an accurate yet efficient computational scheme, designed for the investigation of small biomolecules, to a molecular cluster., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

By mixing primary and secondary alcohols with carboxylic acids just before the supersonic expansion within pulsed Fourier transform microwave experiments, only the rotational spectrum of the ester was observed. However, when formic acid was mixed with tertiary alcohols, adducts were formed and their rotational spectra could be easily measured. Quantum mechanical calculations were performed to interpret the experimental evidence., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Upon supersonic expansion, formic acid and cyclobutanone (CBU) form a molecular cluster in which the two constituent molecules, linked by OHO and CHO hydrogen bonds, undergo a rapid interconversion between two equivalent forms. The tunneling motion takes place through the rupture and reformation of the C-HO hydrogen bond between the carbonyl oxygen of HCOOH and one of the two hydrogen atoms of the methylenic group adjacent to the cyclobutanone keto group. From the microwave spectra, tunneling energy splittings (ΔE 01 ) have been determined for the parent (1122.756(3) MHz), DCOOHCBU (1084.538(1) MHz) and HCOODCBU (1180.282(4) MHz) isotopic species. From these splittings, the potential barrier to interconversion has been calculated to be B 2 = 39.7(5) cm -1 . The tunneling pathway is an asymmetric butterfly-like motion between the two moieties of the adduct, with a barrier at a configuration in which the ring plane of cyclobutanone is coplanar with formic acid.

The rotational spectra of two conformers of the 1 : 1 adduct of fluoroacetic acid with water have been assigned by pulsed jet Fourier transform microwave spectroscopy. Their shapes differ according to the trans and cis forms of the fluoroacetic acid moiety. This is in contrast to the rotational spectrum of the monomer, for which the cis form has not been observed. Details of the hydrogen bond, structure, dynamics and energetic features of the two species are given.

The rotational spectra of four isotopologues of the 1:1 complex between formic acid and pyridine show that the two units are linked together through a "classical" (OH···N) and a weak (CH···O) hydrogen bond. The molecular system appears quite rigid and no effects of the internal motions have been observed in the spectrum. The dissociation energy obtained from the centrifugal distortion by applying an approximate model, 39.8 kJ/mol, is quite similar to the ab initio value, 41.7 kJ/mol. Its relatively high value suggests a small charge transfer to take place.

The rotational spectra of the parent species and of four water isotopologues (-DOH, -HOD, -DOD, and -H(18)OH) of the adduct 3-fluoropyridine-water have been investigated using pulsed supersonic-jet Fourier-transform microwave spectroscopy. From the rotational constants, the structure of the adduct was deduced where the water is linked to the aromatic ring through an intermolecular O-H···N hydrogen bond with a bond distance of 1.9961(5) Å and an O-H···N angle of 156.8(1)°. The shape of the complex is such that the water oxygen is in the plane of the aromatic ring, on the opposite side of fluorine, and forming a C-H···N weak hydrogen bond with the adjacent aromatic hydrogen.

The rotational spectra of two isotopologues of chlorotrifluoroethylene-dimethyl ether show that the two constituent molecules are held together by a lone pair···π interaction. The ether oxygen is linked to the (CF2) carbon atom, with a C-O distance of 2.908 Å.

The National Project RITMARE (la Ricerca ITaliana per il MARE-Italian Research for the sea) started from 1 January 2012. It is one of the national research programs funded by the Italian Ministry of University and Research. RITMARE is coordinated by the National Research Council (CNR) and involves an integrated effort of most of the scientific community working on marine and maritime issues. Within the project, different marine study areas of strategic importance for the Mediterranean have been identified: Among these, the coastal area of Taranto (Ionian Sea, Southern Italy) was chosen for its different industry settlements and the relative impact on the marine environment. In particular, the research has been concentrated on the Mar Piccolo of Taranto, a complex marine ecosystem model important in terms of ecological, social, and economic activities for the presence also of extensive mussel farms. The site has been selected also because the Mar Piccolo area is a characteristic "on field" laboratory suitable to investigate release and diffusion mechanisms of contaminants, evaluate chemical-ecological risks towards the marine ecosystem and human health, and suggest and test potential remediation strategies for contaminated sediments. In this context, within the project RITMARE, a task force of researchers has contributed to elaboration a functioning conceptual model with a multidisciplinary approach useful to identify anthropogenic forcings, its impacts, and solutions of environmental remediation. This paper describes in brief some of the environmental issues related to the Mar Piccolo basin.

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment-water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m(-2) day(-1)) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.

Knowledge on ecosystem functioning can largely contribute to promote ecosystem-based management and its application. The Mar Piccolo of Taranto is a densely populated area at a high risk of environmental crisis. Here, planktonic primary production (PP) and heterotrophic prokaryotic production (HPP) were measured as proxies of functioning in three sampling sites located in two inlets at different levels of industrial contamination, during three sampling surveys (June 2013, February and April 2014). To have a better overall view and provide some insights into the benthic-pelagic coupling, we integrated PP and HPP in the water column with those in the sediments and then discussed this with the origin of the organic matter pools based on analysis of stable isotopes. Heavy metals and polychlorobiphenyls (PCBs) were also analysed in the surface (1 cm) sediment layer and related to the overall ecosystem functioning. Multidimensional scaling (MDS) analysis, based on the main data, clearly separated the second inlet from the first one, more severely impacted by anthropogenic activities. The stable isotope mixing model suggested the prevalent terrestrial/riverine origin of the particulate organic matter pools (mean 45.5 %) in all sampling periods, whereas phytoplankton contributed up to 29 % in February. Planktonic PP and HPP rates followed the same pattern over the entire study period and seemed to respond to phytoplankton dynamics confirming this community as the main driver for the C cycling in the water column. On the contrary, benthic PP rates were almost negligible while HPP rates were lower or comparable to those in the water column indicating that although the Mar Piccolo is very shallow, the water column is much more productive than the surface sediments. The sediment resuspension is likely responsible for a pulsed input of contaminants into the water column. However, their interference with the proper functioning of the pelagic ecosystem seems to be limited to the bottom layers.

Concentrations of some metals (Cd, Cu, As, Hg, Pb) and polychlorinated biphenyls (PCBs) were investigated in edible marine organisms from different trophic levels and feeding behaviour like bivalve molluscs (Mytilus galloprovincialis and Chlamys glabra), gastropod molluscs (Hexaplex trunculus) and some commercial species of fish (Trachurus trachurus, Boops boops, Sarpa salpa and Gobius niger). These species were collected in the first inlet of the Mar Piccolo of Taranto (Ionian Sea, Southern Italy), classified as 'Site of National Interest' established by National Law 426 (1998) and included in the 'National Environmental Remediation and Restoration Projects'. The aim of this work was to investigate contamination levels and public health risks, associated with consuming seafood harvested from these areas. Moreover, in this study, was also estimated the weekly intake in children and adults, both for metals and PCBs. In comparison with the permissible limits set by EC Regulations, Cd and Pb levels were over the limit in the H. trunculus (in all sampling stations) and in the fish T. trachurus respectively. PCBs were over the legal limit in all sampled species with the exception of M. galloprovincialis (station 1), C. glabra and the herbivorous fish S. salpa. In the fish T. trachurus, for example, the concentration of six target PCBs was about five times higher than the EC limit. The estimated intakes of those trace elements included in this study through seafood consumption by the population exceed the provisional tolerable weekly intake recommended by the Joint FAO/WHO Expert Committee on Food Additives for Cd and Hg in the H. trunculus and T. trachurus, especially in children. Moreover, hazard quotience (HQ) for Hg and Cd was >1 in the children for T. trachurus and H. trunculus consumption. As regard non-dioxin-like PCB (NDL-PCB), the estimated intake were always above the 'provisional guidance value' (70 ng/kg body weight) Arnich et al. (Regul Toxicol Pharm 54: 287-2, 2009) for all sampled organism. Thus, health risks due to the dietary Hg, Cd and PCBs intake, especially for children, cannot be excluded. Therefore, an extended remediation programme is necessary to safeguard marine ecosystem, human health and, not less important, the economic activities, in the Taranto marine area.

The effects of sediment resuspension on the fate of metals and polychlorinated biphenyls (PCBs) were studied by using a short-term small reactor. Sediments and water were collected nearby the most contaminated site of the Mar Piccolo of Taranto. Contaminant partitioning was calculated between the solid and water phases and, in the latter, between the dissolved and particulate phases and related to physical-chemical variables. Before and after resuspension, metal concentrations in sediments did not vary remarkably. Except for Cd, all the analyzed metals exceeded by many folds both threshold effect level (TEL) and probable effect level (PEL) SQGs. Igeo index values for Hg designated the sediment quality as extremely polluted for Pb, Cu and moderately polluted for Zn. In the dissolved phase, Mn increased of about 70 times, Fe of about 7 times and Hg and Zn of 4 and 3 times, respectively. PCBs in sediments before and after resuspension did not vary for more than 15 %. PCB concentrations exceeded for more than ten times PEL values. After resuspension, PCBs increased from 0.82 to 4.82 ng L(-1) in the dissolved phase and from 0.22 to 202.21 ng L(-1) in the particulate one. The dissolved phase was initially enriched in light- to mid-weight compounds. After resuspension, the particulate phase was enriched in heavier congeners. In particular, hexachlorobiphenyl-153, 149 and 138 together with heptachlorobiphenyl-180 and 187 accounted for 57 % of total PCBs. The dissolved organic carbon (DOC) that increased from 1.31 to 8.55 mg L(-1) likely influenced the fate of metals and PCBs in the dissolved and particulate phases. Despite that the residence time of the contaminated resuspended sediments in the water column is limited, they are still highly toxic for the pelagic trophic web.

The rotational spectra of four conformers (At, Ag, Et, Eg) of the tertiary alcohol 1-methylcyclohexanol were assigned by pulsed jet Fourier transform microwave spectroscopy. The transitions of two gauche conformers were split in two separated component lines, but it was not possible-from the available measured transitions-to accurately determine their vibrational ΔE0+0- ground-state splittings, respectively. In addition, the rotational spectra of the four OD deuterated isotopologues were measured and assigned. For the gauche species of this isotopologue we were able to determine the tunneling splittings, ΔE0+0-(Ag, OD) = 15.581(5) GHz and ΔE0+0-(Eg, OD) = 18.17(3) GHz, respectively. From these splittings the inversion barriers for Ag and Eg were determined, by using a flexible model, to be B2(Ag) = 356(10) and B2(Eg) = 320(10) cm(-1), respectively.

Formic acid and dimethyl ether are combined in a supersonic expansion to form a molecular adduct with the two subunits held together by a "classical" OH···O hydrogen bond and a bifurcated weak CH2···O hydrogen bond. The rotational spectra of the parent and of two (13)C isotopologues in natural abundance show that the complex has Cs symmetry, with the heavy atom symmetry planes of HCOOH and (CH3)2O perpendicular to each other.

The investigation of an isolated ribofuranose unit in the gas phase reveals the intrinsic conformational landscape of the biologically active sugar form. We report the rotational spectra of two conformers of methyl β-d-ribofuranoside in a supersonic jet expansion. Both conformers adopt a near twisted ((3)T2) ring conformation with the methoxy and hydroxymethyl substituents involved in various intramolecular hydrogen bonds.

The rotational spectra of two tautomers of purine have been measured by pulsed jet Fourier transform microwave spectroscopy coupled to a UV ultrafast vaporization system. The population ratio of the two main tautomers [N(7)H]/[N(9)H] is about 1/40 in the gas phase. It contrasts with the solid state where only the N(7)H species is present, or in solution where a mixture of both tautomers is observed. For both species, a full quadrupolar hyperfine analysis has been performed. This has led to the determination of the full sets of diagonal quadrupole coupling constants of the four (14)N atoms, which have provided crucial information for the unambiguous identification of both species. This work shows the great potential of microwave spectroscopy to study isolated biomolecules in the gas phase. All the work was supported by theoretical calculations.

Background: Nursing students can be exposed to patients with hepatitis A virus (HAV) and can represent a vehicle of transmission both for health personnel, patients and relatives., Objectives: The aim of this study was to assess the risk of HAV infection in nursing students during their internship., Patients and Methods: A seroprevalence survey on HAV infection was performed on nursing students at the Cagliari university-hospital, together with the assessment of the compliance to preventive measures to decrease the risk of infection during their internship. Blood specimens were obtained from 253 students. All serum samples were tested for anti-HAV antibodies (IgG) by the enzyme-linked immunosorbent assay (ELISA). Compliance to preventive measures was recorded by trained personnel., Results: Overall HAV seropositivity in nursing students (mean age 24, range 17 - 45 years) was 3%. Compliance to preventive measures was not uniform (6% - 76%) and extremely low in some specific measures targeted to decrease the oral-fecal transmission., Conclusions: The high proportion of susceptible nursing students can contribute to an increase in the risk of nosocomial transmission, especially when specific preventive measures are not completely applied. Nursing education packages, before starting medical internship, should be implemented in order to increase their compliance to preventive measures, especially in wards at higher risk. Vaccination should be considered in wards at higher risk.

The potential energy surface (PES) of the general anesthetic fluoroxene (2,2,2-trifluoroethyl vinyl ether) was probed in a supersonic jet expansion using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy and theoretical calculations. The PES is dominated by a single conformation, as other stable minima are shown to kinetically relax in the expansion to the global minimum. Consistently, the rotational spectrum reveals a single conformation. Fluoroxene adopts a CS heavy-atom planar skeleton structure in the gas phase, with a cis-trans conformation (cis for the CH2=CH-O-CH2- and trans for the =CH-O-CH2-CF3 part). The sensitivity of a recently-built CP-FTMW spectrometer at the UPV/EHU is demonstrated by the detection of five isotopologues of fluoroxene in natural abundance, corresponding to the (13)C and (18)O monosubstituted species. The rS and r0 structures were determined and are in good agreement with theoretical predictions using the MP2, B3LYP and M06-2X methods.

The structural and energetic features of the C-H⋅⋅⋅π interaction and the internal dynamics of the CHF3 group change drastically in going from benzene-CHF3 to indan-CHF3 , according to the analysis of the rotational spectrum of the latter complex generated in a supersonic expansion., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The rotational spectra of four isotopologues of the 1:1 complex between chloromethane and water revealed the presence of only one rotamer in a pulsed jet expansion. The two subunits are linked through two weak hydrogen bonds, O-H⋅⋅⋅Cl (R(H⋅⋅⋅Cl) =2.638(2) Å) and C-H⋅⋅⋅O (R(H⋅⋅⋅O) =2.501(2) Å), forming a five-membered ring. All transitions display the hyperfine structure due to the (35)Cl (or (37)Cl) nuclear quadrupole effects. Dynamical features in the spectrum are caused by two large-amplitude motions. Each component line appears as an asymmetric doublet with a relative intensity ratio of 1:3. The splittings led to the determination of barrier to internal rotation of water around its symmetry axis, V(2) =320(10) cm(-1). Finally, an unexpected small value of the inertial defect (-0.96 uÅ(2) rather than -3.22 uÅ(2)) allowed the estimation of the barrier to the internal rotation of the CH(3) group, V(3) ≈8 cm(-1)., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The rotational spectra of four isotopologues of the adduct C2F3Cl-NH3 show that NH3 is bound to the partner molecule through a (N)lone-pair···π interaction. Ammonia is located in proximity to the C2 atom (the one linked to two fluorine atoms), with the C2···N distance = 2.987(2) Å. The nuclear hyperfine structure due to the quadrupole coupling effects of (35)Cl/(37)Cl and (14)N nuclei has been fully resolved. The (14)N quadrupole coupling constants allow estimating the effective orientation of NH3 in the complex.

The rotational spectra of two isotopologues of the 1:1 complex between chlorotrifluoromethane and formaldehyde have been recorded and analyzed by using Fourier-transform microwave spectroscopy. Only one rotamer was detected, with the two constituent molecules held together through a Cl⋅⋅⋅O halogen bond (R(Cl⋅⋅⋅O) = 3.048 Å). The dimer displays two simultaneous large-amplitude intramolecular motions. The internal rotation of formaldehyde around its symmetry axis (V2 = 28(5) cm(-1)) splits all the rotational transitions into two component lines with a relative intensity ratio of 1:3. On the other hand, the almost free internal rotation (V3 ≈ 2.5 cm(-1)) of the CF3 symmetric top increases the "rigid" value of the rotational constant A by almost one order of magnitude. In addition, all the transitions display a hyperfine structure due to the (35)Cl (or (37)Cl) nucleus quadrupole effects., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The levels and specific profiles of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in Mytilus galloprovincialis from the Mar Grande and the Mar Piccolo of Taranto were determined during the extensive monitoring plan of Local Health Authority to assess PCDD/Fs and DL-PCBs contamination in food and farm products, within 20 km from the industrial areas of Taranto, between March and December 2011. The average Total Toxicity Equivalence (TEQ) values for the sum of PCDD/F and DL-PCBs ranged from 1.61 to 5.63 pg WHO2005-TEQ g(-1) wet weight basis, with the highest in the first inlet of the Mar Piccolo. In particular, DL-PCBs were the dominant chemicals in all samples, followed by PCDFs and PCDDs. Congener patterns in mussels were similar, indicating a homogeneous behavior in studied areas and, probably, the same type of source. The seasonal concentrations trend showed a relevant increase of dioxin and dioxin-like PCBs TEQs during the summer months, exceeding the limits set by the European Community for food and foodstuff. Reducing PCDD/Fs and PCBs is necessary to decrease contamination levels in order to safeguard marine ecosystem and human health in the Taranto area.

The rotational spectrum of the adduct pyridine-methane shows that methane links to an aromatic molecule apparently through a C-H···π weak hydrogen bond. The shape and the internal dynamics behaviour of this complex are very similar to that of the van der Waals complexes involving aromatic molecules with rare gases.

The pulsed jet Fourier transform microwave spectrum of the 1:1 complex between CF3Cl and CH3F shows that the two moieties are linked by a Cl···F halogen bond (RCl···F = 2.995 Å). The two symmetric tops CF3 and CH3 undergo free or almost free internal rotations, which alter the "rigid" value of the rotational constant A by almost 1 order of magnitude.

The rotational spectra of two isotopologues of a 1:1 difluoromethane-dichloromethane complex have been investigated by pulsed-jet Fourier-transform microwave spectroscopy. The assigned (most stable) isomer has C(s) symmetry and it displays a network of two C-H⋅⋅⋅Cl-C and one C-H⋅⋅⋅F-C weak hydrogen bonds, thus suggesting that the former interactions are stronger. The hyperfine structures owing to (35)Cl (or (37)Cl) quadrupolar effects have been fully resolved, thus leading to an accurate determination of the three diagonal (χ(gg); g=a, b, c) and the three mixed quadrupole coupling constants (χ(gg'); g, g'=a, b, c; g≠g'). Information on the structural parameters of the hydrogen bonds has been obtained. The dissociation energy of the complex has been estimated to be 7.6 kJ mol(-1)., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The rotational spectra of five isotopologues of the 1:1 complex trifluoroanisole-water have been investigated with pulsed jet Fourier transform microwave spectroscopy. The triple fluorination of the methyl group greatly affects the features of the rotational spectrum of the complex with water, with respect to those of the related complex anisole-water. The shape, the internal dynamics, and the isotopic effects turned out to be quite different from those of the anisole-water adduct ( Giuliano , B. M. ; Caminati , W. Angew. Chem., Int. Ed. 2005 , 44 , 603 - 606 ). However, as in anisole-water, water has the double role as a proton donor and proton acceptor, and it is linked to trifluoroanisole through two, O-H···O and C-H···O hydrogen bonds.

The rotational spectra of several isotopologues of the 1:1 complex between the inhaled anesthetic isoflurane and water have been recorded and analyzed by using Fourier transform microwave spectroscopy. The rotational spectrum showed a single rotamer, corresponding to the configuration in which the most stable conformer of isolated isoflurane is linked to the water molecule through an almost linear C-H⋅⋅⋅O weak hydrogen bond. All transitions display a hyperfine structure due to the (35)Cl (or (37)Cl) nuclear quadrupole effects., (Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The pulsed-jet Fourier transform rotational spectra of 4 isotopologues have been recorded for the most stable conformation of the molecular cluster pyridine-CH3F. Two weak C-H···N and C-H···F hydrogen bonds link the two subunits of the complex. Structural information on the hydrogen bridges has been obtained. The internal rotation of the CH3F subunit around its symmetry axis splits all rotational transitions into two (A and E) well resolved component lines, leading to a V3 barrier height of 1.55(1) kJ mol(-1).

This project was carried out to assess the levels and spatial distribution of organochlorine compounds in the coastal marine environment, using mussels as bioindicators to evaluate the coastal water quality. Levels of polychlorobiphenils (PCB), chlorinated pesticides (DDT isomers, HCH isomers, Aldrin, Dieldrin, alfa-Endosulfan, Hexachlorobenzene, Pentachlorobenzene) and polybrominated diphenyl ethers (PBDEs) were determined in tissues from mussels (Mytilus galloprovincialis) collected along the Apulia Region coasts (Mediterranean Sea). Results indicate that contamination by organochlorine compounds is higher in mussels sampled in the Ionian Sea than in those from the Adriatic Sea, with PCB levels up to seven times higher in mussels from Ionian than from the Adriatic Sea. Although PCB levels were above the maximum values indicated by both European Community (EC) and National regulation in several sample sites, the PCB concentrations were particularly high in some stations, suggesting that these locations require a much specific attention. Conversely, results on the mussel contamination by PBDEs highlight their ubiquitous environmental distribution, and underline the need to establish the maximum level for these compounds in foodstuff, according to European Regulations., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Based on hospital discharges in 1001-2010, we calculated risk of tumours with an elevated occupational and environmental etiological fraction by health district of residence within the Local Health Unit (LHU) N. 8 of Sardinia. With reference to the age and gender-specific hospitalization rates of the whole LHU, residents in the urban Cagliari health district showed an excess risk of haemolymphopoietic cancer (RR = 1.07; 95% CI 1.03-1.12) and bladder cancer (RR = 1.10; 95% CI 1.05-1.16); in both instances, risks were higher among female residents. The highest excess risk for lung cancer was observed among residents in the Quartu-Parteolla health district (RR = 1.13; 95% CI 1.05-1.21), and it was slightly higher among male residents. The results appear to confirm the role of urban factors in increasing cancer risk.

Total mercury and methylmercury concentrations were measured in sediments and marine organisms from the Taranto Gulf to understand their distribution and partitioning. Sediment concentrations ranged from 0.036 to 7.730 mg/kg (mean: 2.777 mg/kg d.w.) and from 1 to 40 μg/kg (mean: 11 μg/kg d.w.) for total mercury (THg) and methylmercury (Me-Hg), respectively. In mollusks THg ranged from n.d. to 1870 μg/kg d.w. while in fish from 324 to 1740 μg/kg d.w. Me-Hg concentrations in fish ranged from 190 to 1040 μg/kg d.w. and from n.d. to 1321 μg/kg d.w. in mollusks. THg exceeded the maximum level fixed by the European Commission (0.5 mg/kg w.w.) only in gastropod Hexaplex t. The calculated weekly intake was in many cases over the Provisional Tolerable Weekly Intake established by EFSA for all edible species. These results seem to indicate that dietary consumption of this seafood implicates an appreciable risk for human health., (Copyright © 2011 Elsevier GmbH. All rights reserved.)

Total mercury (THg) and methylmercury (Me-Hg) concentrations were determined in mussels (Mytilus galloprovincialis) from 10 stations located in the Mar Piccolo of Taranto (Ionian Sea, Taranto Gulf) an important semi-enclosed basin in Italy, devoted to mussel culture activities. The obtained results show that THg and Me-Hg concentrations ranged from 0.236 to 0.559 μg g(-1) d.w. and from 0.066 to 0.155 μg g(-1) d.w., respectively. Consequently, the Me-Hg/THg ratios ranged from 17% to 49%. The dietary intake of THg and Me-Hg were studied among children and adults from Taranto (Southern Italy). The estimated weekly intake for THg and Me-Hg was below the Provisional Tolerable Weekly Intake (PTWI) established by European Food Safety Autority (EFSA) for all sampled mussels, though their consumption provides a THg intake in children near the PTWI., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Polychlorinated biphenyls (PCBs) and 17 parent polycyclic aromatic hydrocarbons (PAHs) were determined in surface sediments from nine stations in the Mar Piccolo of Taranto (Ionian Sea, Southern Italy). Total PAH concentrations ranged from 380 to 12,750 microg/kg d.w., while total PCB levels ranged from 2 to 1684 microg/kg d.w.; this values were higher than those found in others marine coastal areas of the Mediterranean Sea. For PAHs, low molecular weight/high molecular weight, phenanthrene/anthracene and fluoranthene/pyrene ratio were used for discriminating between pyrolitic and petroleum origin. Results showed that PAHs were mainly of pyrolitic origin. PCB and PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism. Finally, ERM and PEL quotients were used to evaluate the degree to which chemicals exceed guidelines. Results suggest an ecotoxicological risk for benthic organisms mainly in the first inlet, where high concentrations of PCBs were found in sediments influenced by harbour activities.

Heavy metals concentrations (Cd, Cu, Hg, Pb, Sn and Zn) have been determined monthly in surface sediments from the Mar Piccolo in Taranto (Ionian Sea, Southern Italy. a semi-enclosed marine basin very important from a mussel-culture point of view. In sediments, sulphides, percentage of organic carbon and redox potential were also determined to show possible correlations between metals levels and redox characteristics of marine sediments. Analytical results, elaborated by multivariate statistical techniques, confirm that sediments collected in the first inlet of Mar Piccolo, where shipbuilding activities are present, have a contamination level greater than those collected in the second inlet. For each metal, the geoaccumulation index (Igeo) has been calculated as criterion to evaluate both pollution levels and metals enrichment in examined sediments: Igeo values confirm that the first inlet is an moderately polluted area from Hg and Pb. In any case, high sulphide concentrations and negative values of redox potentials bring to a conclusion that metals are present in sediments, mainly as insoluble sulphides and then as not bioavailable compounds for filter feeders organisms such as mussels.

Eight patients who were subjected to colorectal surgery received 1500 mg metronidazole and another 8 patients 1600 mg tinidazole. The two groups of patients were comparable in respect to age, body size, diagnoses, types of operations, premedication, and anaesthesia. Concentrations of the parent compounds and hydroxy-metronidazole were determined by high pressure liquid chromatography in serum and tissues (subcutaneous fat, rectus abdominal muscle, peritoneum, greater omentum, distal ileum, colon, appendix). The serum and tissue concentrations of metronidazole and tinidazole were within overlapping ranges. Hydroxy-metronidazole but not hydroxy-tinidazole was detected. The total area under the serum curves was 505 (SD: +/- 181) mg . h/l for metronidazole, 137 (+/- 38) mg . h/l for hydroxy-metronidazole, and 810 (+/- 286) mg . h/l for tinidazole. The serum half-life values in the same order were 8.5, 11.2, and 14.2 hours. The distribution volume (Vd,area) were 30.1 liter for metronidazole and 38.8 liter for tinidazole. The range of tissue concentrations were completely overlapping. The two regimens can, consequently, be assessed as pharmacokinetically similar.