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Chromodomain helicase DNA binding protein 4 (CHD4) is an ATPase subunit of the Nucleosome Remodelling and Deacetylation (NuRD) complex that regulates gene expression. CHD4 is essential for growth of multiple patient derived melanoma xenografts and for breast cancer. Here we show that CHD4 regulates expression of PADI1 (Protein Arginine Deiminase 1) and PADI3 in multiple cancer cell types modulating citrullination of arginine residues of the allosterically-regulated glycolytic enzyme pyruvate kinase M2 (PKM2). Citrullination of PKM2 R106 reprogrammes cross-talk between PKM2 ligands lowering its sensitivity to the inhibitors Tryptophan, Alanine and Phenylalanine and promoting activation by Serine. Citrullination thus bypasses normal physiological regulation by low Serine levels to promote excessive glycolysis and reduced cell proliferation. We further show that PADI1 and PADI3 expression is up-regulated by hypoxia where PKM2 citrullination contributes to increased glycolysis. We provide insight as to how conversion of arginines to citrulline impacts key interactions within PKM2 that act in concert to reprogramme its activity as an additional mechanism regulating this important enzyme., Pyruvate kinase M2 (PKM2) activity is regulated by the availability of metabolic intermediates for nucleotide and amino acid synthesis. Here, the authors show that PKM2 citrullination by PADI1 and PADI3 lowers its sensitivity to metabolic inhibitors leading to increased glycolysis and reduced cancer cell proliferation.

The presence of benzene and similar aromatic compounds in civil environments is due to anthropic actions but also to natural sources. Natural gas consists of a gas mixture where benzene and related compounds are usually presents. Thus, the detection of these compounds in natural gas pipelines is of the utmost importance as well as the control of the concentration level, which must remain below the limits consented by law. In this regard, it is of striking interest to engineer devices able to detect these compounds by automatic and continuous remote control. Here, we discuss the application of an optical device designed for the measurement of sulfured odorizing agents in natural gas pipelines aiming at the detection and the measurement of benzene, toluene, and xylenes (BTX) in the same contexts. The instrument consists of a customized UV spectrophotometer connected to an automatic control system able to provide in-field detections of BTX through a continuous and remote check of the gaseous mixture. Relatively to benzene, the instrument is characterized by values of LOD (level of detection) and LOQ (level of quantification) equal to 0.55 and 1.84 mg/Sm3, respectively. Similar limits are found for toluene and xylenes (LOD of 0.81, 1.05, 1.41, and 1.00 mg/Sm3 for toluene, meta-, ortho-, and para-xylene, respectively).

Humic substances (HS) possess redox active groups covering a wide range of potentials and are used by facultative anaerobic microorganisms as electron acceptors. To serve as suitable electron shuttles for anaerobic respiration, HS should be able to re-oxidize relatively quickly to prevent polarization of the surrounding medium. Mediated electrochemical oxidation and decolorization assays, based on the reduction of the radical ion of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS•−) allow to determine the electron donating capacity (EDC) of HS, but uncertainties remain about the reaction time that should be allowed to obtain environmentally meaningful EDC values. In this work, we performed a kinetic analysis of the time trend of the reduction of ABTS•− by HS by Vis and Electron Paramagnetic Resonance (EPR) spectroscopies and by cyclic voltammetry. We found evidences of two concomitant separate mechanisms of electron exchange: a fast and a slow transfer processes which may have different environmental roles. These results can set a base to identify the appropriate conditions for the spectrophotometric determination of the fast and slow components of the EDC of HS.

Background: Uncertainty exists about the optimal schedule of adjuvant treatment of breast cancer with aromatase inhibitors and, to our knowledge, no trial has directly compared the three aromatase inhibitors anastrozole, exemestane, and letrozole. We investigated the schedule and type of aromatase inhibitors to be used as adjuvant treatment for hormone receptor-positive early breast cancer. Methods: FATA-GIM3 is a multicentre, open-label, randomised, phase 3 trial of six different treatments in postmenopausal women with hormone receptor-positive early breast cancer. Eligible patients had histologically confirmed invasive hormone receptor-positive breast cancer that had been completely removed by surgery, any pathological tumour size, and axillary nodal status. Key exclusion criteria were hormone replacement therapy, recurrent or metastatic disease, previous treatment with tamoxifen, and another malignancy in the previous 10 years. Patients were randomly assigned in an equal ratio to one of six treatment groups: oral anastrozole (1 mg per day), exemestane (25 mg per day), or letrozole (2·5 mg per day) tablets upfront for 5 years (upfront strategy) or oral tamoxifen (20 mg per day) for 2 years followed by oral administration of one of the three aromatase inhibitors for 3 years (switch strategy). Randomisation was done by a computerised minimisation procedure stratified for oestrogen receptor, progesterone receptor, and HER2 status; previous chemotherapy; and pathological nodal status. Neither the patients nor the physicians were masked to treatment allocation. The primary endpoint was disease-free survival. The minimum cutoff to declare superiority of the upfront strategy over the switch strategy was assumed to be a 2% difference in disease-free survival at 5 years. Primary efficacy analyses were done by intention to treat; safety analyses included all patients for whom at least one safety case report form had been completed. Follow-up is ongoing. This trial is registered with the European Clinical Trials Database, number 2006-004018-42, and ClinicalTrials.gov, number NCT00541086. Findings: Between March 9, 2007, and July 31, 2012, 3697 patients were enrolled into the study. After a median follow-up of 60 months (IQR 46–72), 401 disease-free survival events were reported, including 211 (11%) of 1850 patients allocated to the switch strategy and 190 (10%) of 1847 patients allocated to upfront treatment. 5-year disease-free survival was 88·5% (95% CI 86·7–90·0) with the switch strategy and 89·8% (88·2–91·2) with upfront treatment (hazard ratio 0·89, 95% CI 0·73–1·08; p=0·23). 5-year disease-free survival was 90·0% (95% CI 87·9–91·7) with anastrozole (124 events), 88·0% (85·8–89·9) with exemestane (148 events), and 89·4% (87·3 to 91·1) with letrozole (129 events; p=0·24). No unexpected serious adverse reactions or treatment-related deaths occurred. Musculoskeletal side-effects were the most frequent grade 3–4 events, reported in 130 (7%) of 1761 patients who received the switch strategy and 128 (7%) of 1766 patients who received upfront treatment. Grade 1 musculoskeletal events were more frequent with the upfront schedule than with the switch schedule (924 [52%] of 1766 patients vs 745 [42%] of 1761 patients). All other grade 3–4 adverse events occurred in less than 2% of patients in either group. Interpretation: 5 years of treatment with aromatase inhibitors was not superior to 2 years of tamoxifen followed by 3 years of aromatase inhibitors. None of the three aromatase inhibitors was superior to the others in terms of efficacy. Therefore, patient preference, tolerability, and financial constraints should be considered when deciding the optimal treatment approach in this setting. Funding: Italian Drug Agency.

Epigenetic silencing of promoter and enhancer regions is a common phenomenon in malignant cells. The transcription factor STAT3 is aberrantly activated in several tumors, where its constitutive acetylation accounts for the transcriptional repression of a number of tumor suppressor genes (TSG) via molecular mechanisms that remain to be understood. Using nucleophosmin-anaplastic lymphoma kinase–positive (NPM-ALK+) anaplastic large-cell lymphoma (ALCL) as model system, we found in cells and patient-derived tumor xenografts that STAT3 is constitutively acetylated as a result of ALK activity. STAT3 acetylation relied on intact ALK-induced PI3K- and mTORC1-dependent signaling and was sensitive to resveratrol. Resveratrol lowered STAT3 acetylation, rescued TSG expression, and induced ALCL apoptotic cell death. STAT3 constitutively bound the Sin3A transcriptional repressor complex, and both STAT3 and Sin3A bound the promoter region of silenced TSG via a resveratrol-sensitive mechanism. Silencing SIN3A caused reexpression of TSG, induced ALCL apoptotic cell death in vitro, and hindered ALCL tumorigenic potential in vivo. A constitutive STAT3–Sin3A interaction was also found in breast adenocarcinoma cells and proved critical for TSG silencing and cell survival. Collectively, these results suggest that oncogene-driven STAT3 acetylation and its constitutive association with Sin3A represent novel and concomitant events contributing to STAT3 oncogenic potential. Significance: This study delineates the transcriptional regulatory complex Sin3A as a mediator of STAT3 transcriptional repressor activity and identifies the STAT3/Sin3A axis as a druggable target to antagonize STAT3-addicted tumors.

Understanding the extent to which laboratory findings of low pH on marine organisms can be extrapolated to the natural environment is key toward making better projections about the impacts of global change on marine ecosystems. We simultaneously exposed larvae of the sea urchin Arbacia lixula to ocean acidification in laboratory and natural CO2 vents and assessed the arm growth response as a proxy of net calcification. Populations of embryos were simultaneously placed at both control and volcanic CO2 vent sites in Ischia (Italy), with a parallel group maintained in the laboratory in control and low pH treatments corresponding to the mean pH levels of the field sites. As expected, larvae grown at constant low pH (pHT 7.8) in the laboratory exhibited reduced arm growth, but counter to expectations, the larvae that developed at the low pH vent site (pHT 7.33–7.99) had the longest arms. The larvae at the control field site (pHT 7.87–7.99) grew at a similar rate to laboratory controls. Salinity, temperature, oxygen and flow regimes were comparable between control and vent sites; however, chlorophyll a levels and particulate organic carbon were higher at the vent site than at the control field site. This increased food availability may have modulated the effects of low pH, creating an opposite calcification response in the laboratory from that in the field. Divergent responses of the same larval populations developing in laboratory and field environments show the importance of considering larval phenotypic plasticity and the complex interactions among decreased pH, food availability and larval responses.

Commercial kiwifruit (Actinidia chinensis) cultivars include both green-fleshed and yellow-fleshed fruit. While both types are green-fleshed during the early stages of fruit development, the yellow-fleshed fruit undergo a marked green to yellow transition associated with degradation of chlorophyll (degreening). To better understand the postharvest temperature sensitivity of the degreening process on off-vine fruit, three kiwifruit cultivars were selected: ‘Zesy003’, ‘Zesh004’ and ‘Hayward’, each having a different degreening behaviour. ‘Zesy003’ is marketed as a yellow-fleshed fruit and ‘Hayward’ and ‘Zesh004’as green-fleshed, despite the significant degreening of the last cultivar late in development. The degreening responses of harvested fruit of the three cultivars to a range of temperatures (1 °C–15 °C) were quantified both by flesh-colour measurement and by analysing the expression of the genes for the main enzymes involved in the chlorophyll degradation pathway. Using the newly annotated kiwifruit genome, sequences for genes involved in chlorophyll metabolism were determined, including STAY GREEN 2 (SGR2), PHEOPHORBIDE HYDROLASE 1 (PPH1), PHEOPHORBIDE A OXYGENASE (PAO1) and RED CHOROPHYLL CATABOLITE REDUCTASE (RCCR) and their expression compared. In spite of the inherently different degreening patterns of the three cultivars, all responded similarly to temperature, showing a faster flesh-colour change at high temperature and a slower or absent colour change at low temperature. In absolute terms, fruit of ‘Zesy003’ degreened faster than ‘Zesh004’ or ‘Hayward’. Expression of two genes involved in the chlorophyll degradation pathway, PAO1 and SGR2, was higher in ‘Zesy003’ than in ‘Zesh004’ or ‘Hayward’. SGR2 expression in ‘Zesy003’ was temperature sensitive: it decreased rapidly following harvest, with colder temperatures causing a more rapid down regulation. Likewise PAO1 expression was reduced at lower temperatures. Given the demonstrated activity of SGR2 (and PAO1), this suggests that these genes are important in regulating chlorophyll degradation in yellow-fleshed kiwifruit and partially account for temperature sensitivity.

The Fourier transform infrared (FTIR) spectrum of vinyl fluoride, H2C=CHF, has been widely investigated in the region of the ν4+ν7 combination band around 2800 cm−1 at a resolution of 0.005 cm−1. This vibration of A' symmetry gives rise to an a/b-hybrid band with a predominant a-type component. The rovibrational structure is strongly perturbed and the analysis has been rather complicated since this combination band is involved at least in a seven-level interacting polyad, including the ν8+2ν10, 2ν8+ν10, 2ν7+ν9, ν7+ν8+ν12, ν5+ν9+ν10 and ν7+ν10+ν12 vibrational states. The study has been further complicated by the absence of transitions coming from the perturbers that were considered as dark states. The spectral analysis resulted in the identification of 936 transitions with J" ≤ 46 and Ka" ≤ 11, all belonging to the a-type component. Most of the assigned data have been fitted using the Watson's A-reduction Hamiltonian in the Ir representation and proper Coriolis perturbation operators. The model employed includes seven different resonances within a complex polyad resonant system and a set of spectroscopic constants for the ν4+ν7 combination band, for the dark states, and Coriolis coupling coefficients have been determined.

CHD3 and CHD4 are mutually exclusive ATPase subunits of the Nucleosome Remodelling and Deacetylation (NuRD) complex that regulates gene expression. CHD4 is essential for growth of multiple patient derived melanoma xenografts and for breast cancer. Here we show that CHD4 regulates expression of PADI1 (Protein Arginine Deiminase 1) and PADI3 in multiple cancer cell types modulating citrullination of three arginines of the allosterically-regulated glycolytic enzyme pyruvate kinase M2 (PKM2). Citrullination reprograms cross-talk between PKM2 ligands lowering its sensitivity to the inhibitors Tryptophan, Alanine and Phenylalanine and promoting activation by Serine. Citrullination thus bypasses normal physiological regulation by low Serine levels to promote excessive glycolysis defining a novel pathway regulating proliferation of melanoma and other cancer cells. We provide unique insight as to how conversion of arginines to citrulline impacts key interactions within PKM2 that act in concert to reprogram its activity as an additional mechanism regulating this important enzyme.

The experimental results of Metal-graphene (M-G) contact resistance R C have been investigated in-depth by means of Density Functional Theory (DFT). The simulations allowed us to build a consistent picture explaining the R C dependence on the metal contact materials employed in this work and on the applied back-gate voltage. In this respect, the M-G distance is paramount in determining the R C behavior.

Stable carbon and nitrogen isotope analysis (SIA) was used to examine trophic interactions in a naturally acidified shallow coastal CO2 area in the Mediterranean Sea. SIA was helpful to determine the potential effects of ocean acidification (OA) on the interactions of organic matter sources and polychaete consumers, which appear to be tolerant to high pCO2. Mesoherbivore consumers, represented by three polychaete species, Platynereis dumerilii (Audouin and Milne Edwards, 1834) (Nereididae), Polyophthalmus pictus (Dujardin, 1839) (Opheliidae) and Syllis prolifera Krohn, 1852 (Syllidae), are abundant in the low pH conditions of the CO2 vents. Samples of consumers and potential organic matter sources (macroalgae, seagrass and epiphytes) were collected in two periods (May-June and Oct-Nov 2012) in two acidified areas (Castello Aragonese CO2 vents, off Ischia, Italy) and in two control areas. Results suggest a substantial effect of high pCO2 on isotopic composition of both organic matter sources and consumers. The recurring 13C depletion observed in the acidified sites is probably due to an increase in carbon availability and to the exploitation of volcanic-derived dissolved inorganic carbon (DIC) present in the area. The nutritional quality of organic matter sources was higher in low pH stations, where indeed C:N ratios decreased. Despite the occurrence of these effects, the trophic habit of high pCO2 tolerant polychaete consumers seems not to be dramatically affected. Our findings shed the light on how some benthic organisms may respond well to near-future OA conditions, exhibiting high plasticity also in their feeding habits, without being subject to dramatic ecological changes.

We investigated organic matter (OM) quantity, nutritional quality and degradation rates, as well as abundance and biodiversity of meiofauna and nematodes along the deep continental margin off Spitsbergen, in the Svalbard Archipelago. Sediment samples were collected in July 2010 and 2011 along a bathymetric gradient between 600 m and 2000 m depth, and total mass flux measured at the same depths from July 2010 to July 2011. In both sampling periods sedimentary OM contents and C degradation rates increased significantly with water depth, whereas OM nutritional quality was generally higher at shallower depths, with the unique exception at 600 m depth in 2010. Meiofaunal abundance and biomass (largely dominated by nematodes) showed the highest values at intermediate depths (ca 1500 m) in both sampling periods. The richness of meiofaunal higher taxa and nematode species richness did not vary significantly with water depth in both sampling periods. We suggest here that patterns in OM quantity, C degradation rates, and meiofauna community composition in 2011 were likely influenced by the intensification of the warm West Spitsbergen Current (WSC). We hypothesize that the intensity of the WSC inflow to the Arctic Ocean could have an important role on benthic biodiversity and functioning of deep-sea Arctic ecosystems.

The gas-phase infrared spectra of 1-chloro-1-fluoroethene (geminal chloro-fluoroethene, ClFC=CH2, 1,1-C2H2ClF) were recorded at medium resolution in the range 400 - 6400 cm(-1) and the vibrational analysis led to revise the previous assignments for the ν11 (A'' symmetry), ν2 (A' symmetry) and ν1 (A' symmetry) bands. Besides the fundamentals, all the most relevant spectral features were interpreted in terms of overtone and combination bands, thus obtaining an accurate description of the vibrational structure of ClFC=CH2. Accurate measurements of absorption cross section spectra were carried out and integrated band intensity data were determined. High-level ab initio calculations of harmonic and anharmonic force fields thoroughly supported and guided the analysis and the disentangling of the several strongly coupled polyads involving many vibrational levels. Diagonalization of the effective Hamiltonian with the off-diagonal elements involving several Fermi and Darling-Dennison resonance coefficients computed by the theoretical cubic and quartic force constants provided the predicted energy levels in good agreement with the vibrational assignments. The calculated infrared intensities, obtained by taking into account anharmonic corrections, were compared to the accurate experimental absorption cross section data here determined.

Ocean acidification is predicted to have negative effects on marine biota, resulting in the loss of biodiversity and changes in marine ecosystem structure and function. However, some species and life stages may be capable of thriving in low pH conditions, either due to their natural ability to tolerate stressful low pH–high pCO2 conditions and/or alteration of species interactions caused by changes in pH profiles, or due to evolutionary trade-offs. A better understanding of which species may be capable of tolerating ocean acidification can guide future research into the mechanisms for physiological and ecological resilience to future carbon dioxide (CO2) conditions. We investigated the colonization of selected polychaete species along a pH gradient originating from shallow, coastal volcanic CO2 vents (Ischia, Italy). Colonization was quantified by exposing artificial invertebrate collectors attached to the substratum for 30 days during different periods of the year (late spring, fall and late winter). Three species, Amphiglena mediterranea, Platynereis dumerilii and Syllis prolifera, were present and abundant along the gradient throughout the year. All three species were significantly more abundant in the most acidified areas, confirming their high tolerance and capacity to cope with very low pH. Abundances of all three species were compared to data previously collected via collectors suspended in the water column. More individuals were found in the collectors attached to the substratum, suggesting that abundances may have previously been underestimated. This is likely due to the close proximity of these collectors with the natural rocky substratum. All three species exhibited similar temporal variability, consistent with their life cycle and reproductive biology. Our results demonstrate high tolerance of the species for low and variable pH and corroborate their use as robust models to explore the capacity to cope with low pH–high pCO2 conditions, both in the natural vent systems and in the laboratory.

Polychaete worms are known to thrive in extreme environmental conditions, however little is known about how polychaete species will respond to major climatic stressors, such as ocean acidification. Here, we examined the distribution of Fabriciidae (Annelida, Sabellida) species along a gradient of ocean acidification, caused by carbon dioxide (CO2) vent emissions in a shallow, coastal system off the island of Ischia (Tyrrhenian Sea, Italy). A total of 265 specimens of Fabriciidae, representing six species from five genera, were collected along the gradient. Most of the species were found across the entire CO2 gradient, suggesting polychaetes may have a high tolerance for ocean acidification in the future. Two of the species were new to science, and two of the genera were previously unrecorded in the Mediterranean. A full description of the new species Brifacia aragonensis sp. nov. and Parafabricia mazzellae sp. nov. is given, both of which were most abundant in the most acidified areas (pH 6.6–7.2). The geographical distribution and ecology of the new taxa, as well as of the other fabriciid species collected, is discussed. Taxonomic keys to identify the Fabriciidae species currently recorded in the Mediterranean Sea are also provided.

The protein kinase C (PKC) family of enzymes is a regulator of transmembrane signal transduction. There is evidence demonstrating altered activity of some PKC isoforms (PKC-α, PKC-δ and PKC-ζ) in the neurons of brains of Alzheimer's Disease (AD) sufferers, but little is known about their involvement in the intracellular machinery of amyloid β protein-reactive T lymphocytes in AD. By applying a modified “split-well culture system” for Aβ1–42 reactivity, we carried out flow cytometry analysis and biochemical investigations on the possible involvement of PKC-α, PKC-δ and PKC-ζ in the signalling system activated in Aβ-reactive T cells purified from peripheral blood mononucleate cells (PBMC) from healthy subjects and patients with AD. Flow cytometry analysis of Aβ1–42 activated T lymphocytes in the majority of AD patients highlighted a distinct cellular cluster highly expressing phospho-PKC-δ (P-PKC-δ), while most full-blown AD patients highly expressed two distinct P-PKC-δ and phospho-PKC-ζ (P-PKC-ζ) bright sub-populations. The same investigation performed in freshly purified peripheral T lymphocytes, did not highlight any subpopulation, suggesting that the detection of P-PKC-δ and P-PKC-ζ bright subpopulations is specifically linked to Aβ1–42 activated T lymphocytes. The data presented here, therefore, suggest possible novel hallmarks to discriminate between healthy elderly subjects and beginning or full-blown Alzheimer's Disease patients.

International audience; For molecules with C-H bonds, a local mode description of the bonds is often adopted to interpret the C-H stretching overtone spectra, although a representation in terms of normal mode is also possible. Equivalence between the two alternative representations demands simple numerical equations between the normal mode anharmonicity constants xrs and the quartic anharmonic coupling constants Krstu , the so-called x-K relations. The relations appropriate to low symmetry molecules with two non-equivalent C-H bonds (ν1 , ν2), such as XHC=CHY, are derived in this paper. The consequences of these relations are illustrated with a detailed analysis of the C-H stretching overtone region, where the naive application of the relations obtained for more symmetric molecules could lead to a different interpretation of the overtones 2ν1 , 2ν2 and of the combination band ν1 + ν2 . The relations are tested with theoretical calculations for difluoro- and chlorofluoro-substituted ethenes, propadiene, and butatrienes.

Assessment of pollution impact in soil ecosystems has become a priority and interest has grown concerning the use of invertebrates as sentinel organisms. Inhibition of cholinesterase (ChE) activity has a great potential as a biomarker of pesticide exposure, and we evaluated the ChE kinetic parameters in the earthworm Eisenia andrei in the presence of acetylthiocholine (ASCh), proprionylthiocholine (PSCh) and butyrylthiocholine (BSCh). The highest ChE activity was found in the presence of ASCh and PSCh (42.45 and 49.82 nmol min− 1 mg protein− 1, respectively). BSCh was hydrolyzed at a rate of 4.04 nmol min− 1 mg protein− 1, but the time course did not reach a plateau under our experimental conditions. Km values were 0.142 ± 0.006 and 0.183 ± 0.053 mM for ASCh and PSCh, respectively. ASCh and PSCh hydrolysis were significantly inhibited by eserine (IC50 values were 1.44 × 10− 8 and 1.20 × 10− 8 M, respectively) and by carbaryl (IC50 values of 5.75 × 10− 9 and 4.79 × 10− 9 M). The presence of different ChEs in tissues from E. andrei was assessed by using selective inhibitors for AChE (BW284c51) and BChE (iso-OMPA). BW284c51 strongly reduced ASCh and PSCh hydrolysis and slightly affected that of BSCh, while iso-OMPA was without effect in all cases.

Many factors are involved in the pathogenesis of Alzheimer's disease (AD), and inflammatory-immunlogic activation seems to play a major role. One strategy for treatment of AD has been to use acetylcholinesterase (AChE) inhibitors to increase the levels of acetylcholine and enhancing cholinergic activity in the affected regions of the brain. Cholinergic compounds modulate the immune system, therefore secretion, by peripheral blood mononuclear cells (PBMC), of cytokines was investigated in age-matched controls and in AD patients. Cytokines released by PBMC from AD patients enrolled as pre-treatment patients (T0) and as post-treatment with AchEI (T1), were detected by ELISA assay. The result showed an increase in oncostatin M, interleukin-1β (IL-1β) and interleukin-6 (IL-6) secretion in AD patients compared to healthy controls, and a decrease of cytokine levels in each AD patients treated for 1 month with an acetylcholinesterase inhibitor (AchEI). In conclusion, the results of this study show that the complex pathology in AD may be reflected in a pattern of altered cytokine secretion from PBMC.

For the first time the millimeter-wave spectra of the trans-35ClHC=CHF and trans-37ClHC=CHF isotopomers have been observed in natural abundance. Many DeltaJ=0, +/-1 DeltaK(-1)=+1 transitions for 35ClHC=CHF and DeltaJ=0 DeltaK(-1)=+1 transitions for 37ClHC=CHF have been detected and assigned. This allowed us to accurately determine the vibrational ground-state rotational constants, quartic and some sextic centrifugal distortion constants, and nuclear quadrupole coupling constants for both 35Cl and 37Cl. The experimental investigation has been supported by highly accurate theoretical predictions. As far as ab initio computations are concerned, the complete set of cubic and quartic force constants have been evaluated by numerical differentiation of the analytic second-order Møller-Plesset many-body perturbation theory/correlation consistent polarized valence triple zeta second derivatives. The anharmonic part of the force field completes the theoretical study on the equilibrium structure, dipole moment, chlorine quadrupolar tensor, and harmonic force field previously carried out by the same authors.

Cytokines appear to be involved in the pathogenesis of Alzheimer's Disease (AD). Their modulation by treatment has been investigated only in a few studies. The aim of our study was to evaluate the effect of acetylcholinesterase inhibitors (AChEI) on Interleukin-4 (IL-4) production in AD patients. IL-4 levels were measured by ELISA on peripheral blood mononuclear cell cultures in the presence or absence of Concanavalin A or Phytohaemagglutinin. Linear regression analysis shows that patients who have been treated, have higher levels of IL-4 independently from age, gender and comorbidity. The increased production of IL-4 in AChEI treated patients might represent an additional mechanism through which AChEI act on AD progression. Keywords Interleukin-4; Cytokines; Acetylcholinesterase inhibitors; Alzheimer's disease; Aging

A comparative analysis of polychaete species, classified as motile and low-motile forms, highlighted that the former were characterized not only by a higher metabolic rate (MR), but also by a higher genomic GC content. The fluctuation of both variables was not affected by the phylogenetic relationship of the species. Thus, present results further support that a very active lifestyle affects MR and GC at the same time, showing an unexpected similarity between invertebrates and vertebrates. In teleosts, indeed, a similar pattern has been also observed in comparisons of migratory and nonmigratory species. A cause-effect link between MR and GC has not yet been proved, but the fact that the two variables are significantly linked in all the organisms so far analyzed is, most probably, of relevant biological and evolutionary meaning. The present results fit very well within the frame of the metabolic rate hypothesis proposed to explain the DNA base composition variability among organisms. On the contrary, the thermostability hypothesis was not supported. At present, no data about the recombination rate in polychaetes were available to test the biased gene conversion (BGC hypothesis).

Ionic surfactants such as sodium dodecyl sulfate (SDS) belong to the amphiphile family: they possess a long hydrophobic hydrocarbon chain and a polar hydrophilic headgroup. In a polar solvent and over the critical micellar concentration these molecules join to form micelles. The micellar solutions, in turn, if doped with various ligands tend to aggregate. Solid SDS, micelles of SDS in water and micelles of SDS doped with two types of macrocyclic ligands, Kryptofix 2.2.2 (K222) and crown ether 18-Crown-6 (18C6), at different concentrations are studied by Raman scattering, that represents a new approach to such systems. The experimental Raman spectrum, obtained on crystalline powders of SDS, is compared with the ab initio computed spectrum in order to assign the vibrational bands. After discriminating sensitive peaks by comparing the crystalline powders of the single components and their water solutions, the aggregation process and the action of the ligands are analyzed following the evolution of the intensity and wavenumber of these characteristic Raman peaks. This shows that Raman spectroscopy is sensitive to the aggregation dynamics and to the effects induced by the hydration layer on the molecules in solutions. A saturation effect in the aggregation process with the increase of the ligand concentration is observed. Copyright © 2012 John Wiley & Sons, Ltd.

Eutrophication enhances organic C inputs to the sea bottom, so that the quantity and biochemical composition of sedimentary organic matter are expected to change under different trophic status conditions. In turn, changes in the trophic status are often associated with shifts in the abundance and community structure of the benthos. We investigated the quantity and biochemical composition (protein, carbohydrate, lipid and phytopigment) of sedimentary organic matter together with abundance and community structure of meiofauna in two regions of the Mediterranean Sea characterized by different levels of primary productivity. At each region, five transects were randomly selected along the coastline. At each transect, three stations located at increasing distance from the shore and different water depth were investigated. Uni- and multivariate analyses of variance revealed that the quantity and biochemical composition of sediment organic matter displayed the most relevant differences between stations, suggesting their potential use as descriptor of the benthic trophic state at the small spatial scale (i.e.

The possible effects of ocean acidification on the calcareous skeleton of the Mediterranean bryozoan Myriapora truncata (Pallas, 1766) were studied by transplanting live and dead colonies into an area of natural volcanic CO2 vents at Ischia (Gulf of Naples, Tyrrhenian Sea), Italy. Morphology and geochemistry were compared between colonies from normal (mean pH = 8.07, min. pH 7.95), below-normal (mean pH 7.66, min. pH 7.32) and acidic (mean pH 7.43, min. pH 6.83) conditions after colonies had been exposed in situ for 45 and 128 days. Both distal (juvenile) and proximal (adult) parts of the branches were investigated. Skeletons of live colonies in acidic pH site after 45 days of exposure were less corroded than those of dead colonies, suggesting that the organic tissues enveloping the skeleton play a protective role. Colonies remained alive at the below-normal and acidic pH sites during the 45-day experiment but corrosion was very striking after 128 days, with colonies from the acidic site showing significant loss of skeleton. Compared to the control, these colonies also had lower levels of Mg (mean 8 versus 9.5 wt% Mg) within their skeletons. Electron microprobe mapping showed Mg to be higher in the outer layers of the skeletal walls in colonies from the normal pH site. Corrosion of outer layers of the walls probably explains the lower Mg level found in colonies exposed to acidic conditions. As solubility of calcite increases with Mg content, the enrichment of Mg in outer layers of the skeleton should enhance the vulnerability of Myriapora truncata to dissolution. These findings raise concerns over the survival of bryozoans with Mg calcite skeletons in the face of predicted decreases in oceanic pH levels.

The gas-phase infrared spectrum of monodeuteromethyl bromide, CH2DBr, has been examined at medium resolution in the range 400-10000 cm(-1), leading to the identification of 70 vibrational transitions. The assignment of the absorptions in terms of fundamentals, overtones, combinations, and hot bands, assisted by quantum chemical calculations, is consistent all over the region investigated. The (79/81)Br isotopic splitting for the lowest fundamental nu6 and the value for the v8 = 1 level have been now precisely determined. Anharmonic resonances are very marginal for all fundamentals and the Coriolis interaction effects are clearly evident in the nu4/nu8 band system, in the nu2 and nu7 fundamentals. Spectroscopic parameters, obtained from the analysis of partially resolved rotational structure, have been derived in the symmetric tops limit approximation. High-quality ab initio calculations have been performed, and harmonic and anharmonic force fields have been predicted from coupled cluster CCSD(T) calculations employing the cc-pVTZ basis set. A good agreement between computed and experimental data, also including the C-H stretching overtones at 6000 and 9000 cm(-1), has been obtained.

Aqueous sodium dodecyl sulfate micellar solutions were investigated by a recently developed double-differential dielectric spectroscopy technique in the frequency range 100 MHz–3 GHz at 22 °C, in the surfactant concentration range 29.8–524 mM, explored for the first time above 104 mM. The micellar contribution to dielectric spectra was analyzed according to three models containing, respectively, a single Debye relaxation, a Cole–Cole relaxation and a double Debye relaxation. The single Debye model is not accurate enough. Both Cole–Cole and double Debye models fit well the experimental dielectric spectra. With the double Debye model, two characteristic relaxation times were identified: the slower one, in the range 400–900 ps, is due to the motion of counterions bound to the micellar surface (lateral motion); the faster one, in the range 100–130 ps, is due to interfacial bound water. Time constants and amplitudes of both processes are in fair agreement with Grosse's theoretical model, except at the largest concentration values, where interactions between micelles increase. For each sample, the volume fraction of bulk water and the effect of bound water as well as the conductivity in the low frequency limit were computed. The bound water increases as the surfactant concentration increases, in quantitative agreement with the micellar properties. The number of water molecules per surfactant molecule was also computed. The conductivity values are in agreement with Kallay's model over the whole surfactant concentration range.

Light scattering, UV-visible absorption and UV laser excited fluorescence measurements were performed in rich laminar premixed flames in order to assess the contribution of soot and other organic aerosols to the particulate produced in flames. UV absorbing nanoparticles with a typical size of about 6 nm were detected in situ in the early region of the flame, before soot inception. These particles are almost transparent to the visible radiation. A new sampling system based on water spraying allowed the stabilisation of these particles in aqueous suspension. The UV spectral characteristics of these structures were in excellent agreement with those obtained in flame. A particulate sampling, in the soot forming regime allowed the distinction between the absorption due to soot particles to that due to the nanoparticles still present in the burned gas region. The UV-visible absorption spectrum due to these aerosols has been interpreted in terms of Tauc optical band gap thus allowing a better qualification of both classes of aerosols which is of interest also in the identification of carbon containing particles in the atmosphere. (C) 1998 Elsevier Science Ltd. All rights reserved.

Due to their topographic features, submarine canyons are generally sites of intense shelf-slope exchanges of water and material, fuelling the deep basins with large quantities of sediment exiting from the continental shelf. In order to provide new insights about the role of submarine canyons in controlling the relationships between food availability and benthic biodiversity patterns along the continental slope, we investigated the quantity and the biochemical composition of sediment organic matter and the abundance of meiofaunal assemblages in the sediments along two different branches of a canyon and in an adjacent open slope located in the Bari margin (Adriatic Sea). Our results highlight that even twin branches within the same canyon may exhibit very large differences in the quantity, depth-related patterns and biochemical composition of sediment organic matter as well as of meiofaunal abundance. We also report here that the trophic relationships in the canyon sediments are tightly connected with the h...

A water-in-oil microemulsion composed of water, AOT and decane with volume fraction φ=0.50 and molar ratio X=40.8 was analysed by DSC. The percolation and the bicontinuous transitions as well as the melting endotherms and the freezing exotherms were measured. The main attention was focussed on the system energy balance. It was found that, by freezing the samples after the occurrence of the percolative transition, the total heat released is significantly less than the heat absorbed in the melting endotherms. A simple geometrical model was used as an analysis tool of the aforementioned energy difference. Since the system studied exhibits a percolative transition of dynamic type, on approaching the percolation threshold temperature (T≤T p) and a static percolation for T≥T p, the structural change from the connecting water-droplet-cluster to a connecting water channel was schematised in the model as a change from a sphere-necklace to a water-cylindrical channel of equal volume and equal length. The surface energy associated with the formation of the two different geometrical surfaces was evaluated and the amount of saved energy compared with the experimentally measured one.

We report results from a heterodyne-detected transient grating experiment on a three-component microemulsion system, consisting of water-AOT-decane. We studied the microemulsion characterized by a water-to-AOT ratio of X = 40.8 and a volume fraction phi = 0.50, in a temperature range around the percolation threshold. The measurements have been performed with two exchanged momenta q approximate to 1 and 2 mu m(-1) corresponding to sound frequencies around NO and 420 MHz. The Measured Sound velocities show small but significant evidence of the percolation transition in the temperature domain.

The fanworm Sabella spallanzanii (Gmelin, 1791) (Annelida, Sabellidae) is considered tolerant to several types of stressors but is generally absent from the CO2 vents. A peculiar characteristic of this species is the elevated content of arsenic in the gills, particularly dimethylarsinic acid (DMA), stored as an anti-predatory compound. In this study, modulation of trace metal levels, chemical speciation of arsenic and oxidative stress biomarkers were quantified in S. spallanzanii after a 30days transplant experiment into naturally acidified conditions in a Mediterranean vent system. No significant bioaccumulation of metals was observed in the thoracic tissues and branchial crowns after the translocation period, whereas variations occurred in the relative abundance of different arsenic compounds with the appearance of inorganic forms. The antioxidant system of translocated polychaetes exhibited a significant decrease of enzymatic activities of both catalase and glutathione peroxidases, and the impairment of the overall capability to neutralize hydroxyl radicals (OH). This highlighted an oxidative challenge primarily on the detoxification pathway of hydrogen peroxide. Overall low pH-elevated pCO2 may have detrimental effects on arsenic metabolism and oxidative status of S. spallanzanii, supporting the hypothesis of species-specific differences in vulnerability to ocean acidification.

Ocean acidification (OA) is occurring at a fast rate, resulting in changes of carbonate chemistry in the oceans and in lowering of the pH. Previous studies have documented significant changes in the antioxidant defenses of marine species in response to OA. Here, selected polychaete species, Platynereis dumerilii, Polyophthalmus pictus and Syllis prolifera, were sampled from a natural CO2 vent system (pH = 7.3) and from a non-venting 'control' site (pH = 8.1), and reciprocally transplanted in these areas for 30 days. Total antioxidant capacity toward different forms of oxyradicals was compared in native and transplanted polychaetes: the aim was to assess whether the environmental conditions at the vent site would act as a prooxidant stressor, and the capability of polychaetes to modulate their antioxidant capacity to counteract a varied oxyradicals formation. None of the investigated species enhanced the antioxidant potential during the experiment. A significant reduction of the capability to neutralize different forms of oxyradicals was observed in P. pictus and, partially, in S. prolifera when transplanted from control to naturally-acidified conditions. On the other hand, populations of P. dumerilii originating from the vent and of S. prolifera from both control and acidified sites, showed higher constitutive antioxidant efficiency toward peroxyl radicals and peroxynitrite, which may allow them to cope with short-term and chronic exposure to higher oxidative pressure without further enhancement of antioxidant defenses. Since low pH - high pCO2 is the greatest environmental difference between the control and the vent sites, we suggest that the pro-oxidant challenge due to such peculiarities may have different biological consequences in different polychaete species. Some appear more susceptible to oxidative effects, while others acquire a long term acclimatization to vent conditions through the enhancement of their basal antioxidant protection.

The consistence of the dark material in interstellar space is still under discussion. Reasonable candidates are structures containing silicon or carbon. In that light it is interesting to know the physical and chemical properties of carbonaceous structures produced in flames and to compare them with the spectroscopical properties of interstellar dust. Light scattering, fluorescence induced by UV laser and light absorption have been employed to analyse phenomenological aspects of formation; destruction and chemical transformation of carbonaceous structures formed in rich premixed Laminar methane-oxygen and ethylene-oxygen flames at atmospheric pressure with different C/O ratio, at and above the soot threshold limit. Light scattering measurements also show that in non-sooting conditions, i.e. in the non-sooting zone of sooting flames or in flames below the soot threshold limit, high molecular mass structures are formed. Absorption spectra measured in non-sooting conditions show a continuous decay from 200 to 300 Dill, while in fully sooting conditions an additional peak at around 235 nm appears. Further information is obtained by laser-induced fluorescence investigations. Here. a broad-band peak with a maximum at around 320 nm is always measurable. Approaching the soot nucleation zone a further broad-band fluorescence emission in the visible. in addition to that in the UV, is observed. All the experimental results produce evidence that the early formation of high molecular mass carbonaceous molecules containing aromatic functionalities with not more than two rings occurs. Their role as soot precursors seems to be connected to their change into higher polycondensed aromatic structures. Our results give a hint that these soot precursors and the interstellar dust are members of the same family of carbonaceous structures.

Relatively few studies have characterized basal content and variability of arsenic in polychaetes, despite the potential importance of this element as a pollutant of marine environments. Even less have investigated the chemical speciation of arsenic, occurring as inorganic and organic forms, which reflect a different biological reactivity of the element. In the present paper we integrate existing literature with new data in order to summarize the status quo on arsenic bioaccumulation in polychaetes. We consider species with different trophic habits, phylogenetic relationships, geographic distribution and ecology. Reported data indicate a high variability in arsenic concentration with levels ranging from

This paper reports a small-angle neutron scattering (SANS) characterization of perfluoropolyether (PFPE) aqueous micellar solutions with lithium, sodium, cesium and diethanol ammonium salts obtained from a chlorine terminated carboxylic acid and with two perfluoroisopropoxy units in the tail (n(2)). The counterion and temperature effects on the micelle formation and micellar growth extend our previous work on ammonium and potassium salts n(2) micellar solutions. Lithium, sodium, cesium and diethanol ammonium salts are studied at 0.1 and 0.2 M surfactant concentration in the temperature interval 28-67 degrees C. SANS spectra have been analyzed by a two-shell model for the micellar form factor and a screened Coulombic plus steric repulsion potential for the structure factor in the frame of the mean spherical approximation of a multicomponent system reduced to a generalized one component macroions system (GOCM). At 28 degrees C, for all the salts, the micelles are ellipsoidal with an axial ratio that increases from 1.6 to 4.2 as the counterion volume increases. The micellar core short axis is 13 A and the shell thickness 4.0 A for the alkali micelles, and 14 and 5.1 A for the diethanol ammonium micelles. Therefore, the core short axis mainly depends on the surfactant tail length and the shell thickness on the carboxylate polar head. The bulky diethanol ammonium counterion solely influences the shell thickness. Micellar charge and average aggregation number depend on concentration, temperature and counterion. At 28 degrees C, the fractional ionization decreases vs the counterion volume (or molecular weight) increase at constant concentration for both C = 0.1 M and C = 0.2 M. The increase of the counterion volume leads also to more ellipsoidal shapes. At C = 0.2 M, at 67 degrees C, for sodium and cesium micelles the axial ratio changes significantly, leading to spherical micelles with a core radius of 15 A, lower average aggregation number, and larger fractional ionization.

The Fourier transform infrared (FTIR) spectrum of vinyl fluoride, H2CCHF, has been deeply investigated in the ν4 band region around 6 μm at a resolution of 0.002 cm−1. This normal mode, of A′ symmetry species and corresponding to the CC stretching motion, yields an a/b hybrid band with a prevalent a-type character. In the present contribution, a systematic investigation is carried out by explicitly taking into account the strong and invasive anharmonic and Coriolis resonances, which perturb all of the ν4 ro-vibrational states. Indeed, the ν4=1 state is involved in a six-level resonant polyad, which, besides ν4 (1656.0 cm−1), comprises the A′ symmetry vibrational states ν7+ν9 (1635.5 cm−1), ν10+ν12 (1641.8 cm−1) and 2ν11 (1733.6 cm−1), as well as the ν8+ν12 (1638.7 cm−1) and 2ν9+ν12 (1683.8 cm−1) combination bands of A″ symmetry. The ro-vibrational analysis led to the assignment of more than 2100 transitions of ν4 with J″≤57 and K a ″ ≤ 16 , and about 1000 ro-vibrational transitions (J″≤47 and K a ″ ≤ 11 ) reaching the ν7=ν9=1 state. 505 transitions of these belong to the ν7+ν9−ν9 hot band, which is located at about 1052.4 cm−1 within the atmospheric window. No features are detected for the remaining vibrational states involved in the polyad, which therefore behave as dark states. By adopting an interaction model involving fourteen different anharmonic and Coriolis resonances, the assigned transitions are simultaneously fitted within the Watson's A-reduction Hamiltonian in the Ir representation up to the sixth power of angular momentum operators. As demonstrated by spectral simulations, the obtained ro-vibrational Hamiltonian well reproduces the ro-vibrational spectrum of vinyl fluoride in the 6 μm region.

Halon 1113 (chlorotrifluoroethene), used in the synthesis of fluorocarbon-based polymers, has been recently detected in the atmosphere and it is a potential source of chlorine atoms. In this work, the vibrational properties of chlorotrifluoroethene are studied in the 125–5000 cm−1 region by coupling Fourier-transform infrared spectroscopy and high-level ab initio calculations. The vibrational analysis is performed over the whole spectral range and band intensities are obtained in the range 400–3100 cm−1. Ab initio calculations of the anharmonic force field are performed at the coupled cluster level of theory employing either cc-pVTZ or ANO basis sets. Vibration perturbation theory is applied to obtain spectroscopic parameters from the computed anharmonic force fields. The present results provide a solid interpretation of chlorotrifluoroethene vibrational spectrum, and they represent a significant reference for future studies on this molecule, being also the first published data on absorption cross sections and ab initio calculations.

Difluoromethane (CH(2)F(2), HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH(2)F(2), providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm(-1). Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm(-1) while intensities are predicted within few km mol(-1) from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν(1)>, |2ν(8)>, |2ν(2)> three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm(-1) region is also demonstrated by spectacular spectral simulations carried out by using the ro-vibrational Hamiltonian constants, and the relevant coupling terms, obtained from the perturbation treatment of the ab initio anharmonic force field. The present results suggest CH(2)F(2) as a prototype molecule to test ab initio calculations and theoretical models.

Phenomenological aspects of formation, destruction, and coagulation of high molecular mass structures formed in the main oxidation zone of rich premixed flames and in rich flames well below the soot threshold limit have been examined. High molecular mass structures transparent to the visible radiation, previously detected in the preinception region of soot forming flames, are also present in flames below the soot formation limit. The onset of ultra-violet fluorescence within the main oxidation zone implies that the formation of these species is a very fast process and can be considered as a ''polymerization'' of small aromatic groups activated by the presence of oxidizing agents. The final concentration of this material falls down as the C/O ratio is decreased and below C/O = 0.35 it is not anymore present. It appears that rich premixed flames present two critical C/O ratios: a first one for soot formation and a lower second one for high molecular mass structure formation. Ultra-violet scattering/extinction technique has indicated that the typical average size of these structures is around 4-6 nm and their overall coagulation rate is very low.

Light scattering, fluorescence, and C2 emission induced by an ultraviolet laser source and uv-visibleabsorption have been used to study the phenomenological aspects of formation, destruction, and chemical transformation of high molecular mass structures formed in rich premixed methane flames at atmospheric pressure. High molecular mass structures are formed in CH4/O2 flames with C/O ratios down to 0.35. This value, corresponding to their formation threshold, is noticeably lower than the soot threshold limit (C/O=0.45). Different flames have been analyzed across the soot threshold limit, varying the C/O ratio and the maximum flame temperature, and no dramatic changes in the properties of the high molecular mass structures have been found in the passage from nonsooting to sooting conditions. Their role as soot precursors seems to be connected to a kinetically controlled passage from aromatic functionalities with one or two rings to higher polycondensed aromatic functionalities more than to a carbonization process of these structures. High molecular mass structures are easily photofragmented by an ultraviolet laser source with high-energypulses, and the consequent C2 emission has been attributed to these structures more than to soot particles. From a practical point of view, the spatial distribution of these potential pollutants, whose toxic properties are largely unknown, can be easily followed in practical diffusion flames by monitoring the 2D fluorescence due to C2 photofragments employing an ultraviolet laser source.

The molecular structures and energetics of diazirine (H 2 CN 2 ), diazirinyl radical (HCN 2 ) and their related cations ( H 2 CN 2 + , HCN 2 + ) have been investigated by means of the coupled-cluster method in conjunction with different basis sets. Core correlation effects and basis set incompleteness have been taken into account in order to obtain best estimates of their equilibrium geometries, C–H bond dissociation energies of diazirine and diazirine cation ( H 2 CN 2 + ) , and ionization potentials of diazirine and diazirinyl radical. Adiabatic as well as vertical ionization potentials have been considered. For all the species studied, harmonic vibrational frequencies have also been evaluated in order to obtain zero-point corrections to both ionization potentials and C–H dissociation energies.

Colonies of the cheilostome bryozoan Schizoporella errata were grown at a site near Ischia Island (Tyrrhenian Sea, Italy) where volcanogenic CO2 emissions lower seawater pH to 7.76, simulating levels of ocean acidification predicted for the end of the present century. Compared with colonies from a control site (mean pH = 8.09), putative defensive polymorphs (avicularia) were significantly fewer, and retarded growth of zooidal basal and lateral walls was evident at the low pH site. The lower proportion of avicularia suggests a switch in resource allocation away from defence to favouring rapid growth. In addition, corrosion of the skeleton was observed in both new and old zooids at the low pH site, and feeding zooids were slightly smaller but had larger orifices for the protrusion of feeding lophophores. These findings corroborate previous studies demonstrating potential dissolution of carbonate skeletons in low pH seawater, while providing new insight into the possible ability of colonial species to respond to ocean acidification by adjusting resource allocation between zooids of different types.

A deep and comprehensive investigation of the vinyl fluoride (CH(2)CHF) spectrum in the atmospheric window around 8.7 mu m is presented. At first, the ro-vibrational patterns are modelled to an effective Hamiltonian, which also takes into account the coupling of the C-F stretching vibration, v(7), with the neighbouring vibrational combination v(9) + v(12). The obtained Hamiltonian gives very accurate simulations and predictions of the ro-vibrational quantum energies. Then, in the main part of the work, an experimental and theoretical study of vinyl fluoride self-broadening collisions is carried out for the first time. The broadening coefficients obtained experimentally are compared with those calculated by a semiclassical theory, demonstrating a significant contribution of collisional coupling effects between lines connecting pairs of degenerate (or nearly degenerate) rotational levels. Finally, the experimentally retrieved integrated absorption coefficients are used to calculate the absorption cross-section of the v(7) normal mode, from which dipole transition moments are derived. The obtained results provide a deep insight into the spectral behaviour of vinyl fluoride, in a spectral region of primary relevance for atmospheric and environmental determinations. Indeed, the data presented constitute an accurate model for the remote sensing, of vinyl fluoride-a molecule of proved industrial importance which can lead to hazardous effects in the atmosphere and affects human's health.

Multiple Sclerosis (MS) is a neurodegenerative autoimmune demyelinating disease affecting young adults. The aetiology still remains a mystery and diagnosis is impaired by the lack of defined molecular markers. Autoimmune response remains the main topic under investigation and recent studies suggest additional non-proteic mediators of brain inflammation such as lipids. We carried out an LC-MS based lipidomics approach to highlight serum lipids profiling in MS. Method was optimised and applied in a preliminary clinical cross-sectional investigation of MS patients vs Healthy Controls (HC) and patients with Other Neurological Diseases (OND). Ten significant metabolites were highlighted and tentatively identified by accurate mass and MS/MS experiments. Our most relevant data show altered level of lyso-glycerophosphatidylcholine (lysoPC) and glycerophosphatidylcholine (PC) species. Total lysoPC/PC ratio showed significant decrease in pathological groups (MS, OND) and, in addition, MS subjects had a relevant decrease of this ratio also in respect to OND. These findings suggest that there may be an altered phospholipid metabolism in MS that can be evaluated in serum. Some of these features are distinctive and may be considered specific for MS. Our lipidomics data show, for the first time, evidence in serum of a relationship between LysoPC/PC ratio and MS. (C) 2011 Elsevier B.V. All rights reserved.

The gas-phase Fourier transform infrared spectra of bromodifluoromethane, CHBrF 2, have been recorded up to 10,100cm -1 with a resolution of 0.5cm 1. All the most relevant absorptions in the overtone region have been ascribed to the CH chromophore. Twenty-six bands involving either the CH-stretching (v 1) and bending (v 2, v 7) modes have been assigned and their relative band strengths have been determined. Vibrational analysis of the corresponding polyads (up to N=7/2) has been performed by means of an effective Hamiltonian that takes into account anharmonic resonances, thus leading to the determination of Fermi and Darling-Dennison coupling terms. The obtained effective spectroscopic parameters were able to quantitatively describe both the position and intensity of all the absorption bands, and also to rationalize the effects and the magnitudes of the various resonances in each polyad. The results obtained using this approach have been compared with those computed using high-quality ab initio electronic structure calculations employing second-order vibrational perturbation theory (VPT2). Overall, satisfactory agreement between the observed and the ab initio computed values was obtained by properly taking into account in the final calculations the relative magnitude of the Fermi and Darling-Dennison resonance effects in each polyad.

The possible effects of ocean acidification on growth, organic tissue and protein pro- file in the bryozoan Myriapora truncata (Pallas, 1766) were studied in samples transplanted along a gradient of different pH conditions in an area of natural volcanic CO2 vents at Ischia Island (Tyrrhenian Sea, Italy). Living colonies from normal (mean pH 8.10), intermediate (pH 7.83) and low (pH 7.32) pH sites were investigated after intervals of 34, 57 and 87 d of exposure. M. truncata formed new and complete zooids at the normal site, whereas at the intermediate and low pH sites, neither partial nor complete zooids were produced. After 34 d at intermediate and low pH condi- tions, the organic cuticle which envelops the skeleton increased in thickness when compared to normal colonies, suggesting a protective role against dissolution of the high-Mg calcite skeleton. Significant changes in the protein profile and expression displayed by samples from intermediate and low pH conditions suggest that M. truncata makes an initial attempt to overcome the decrease in pH by up-regulating protein production but eventually, especially in the lowest pH condition, exhausts biochemical energy to maintain this rate of protein production, leading to eventual death.

Three tin(IV) complexes of 2-benzoylpyridine N(4)-phenylthiosemicarbazone (H2Bz4Ph) were prepared: [Sn(L)Cl3] (1), [BuSn(L)Cl2] (2) and [(Bu)2Sn(L)Cl] (3), in which L stands for the anionic ligand formed upon complexation with deprotonation and release of HCl. The complexes were characterized by a number of spectroscopic techniques. The crystal structures of H2Bz4Ph and complex 3 were determined. The antifungal activity of the ligand and its tin(IV) complexes was tested against Candida albicans. The thiosemicarbazone proved to be more active than the tin(IV) complexes. Copyright © 2003 John Wiley & Sons, Ltd.

Downward fluxes of particulate matter were investigated in the polynya of Terra Nova Bay (western Ross Sea) from February 1995 to December 1997. The main biological components were siliceous phytoplankton (diatoms, silicoflagellates and parmales), abundant faecal pellets of several types and zooplankton (mainly shelled pteropods). Vertical fluxes of particles occurred mainly through diatoms and faecal pellets in the first and second part of the summer, respectively. The highest fluxes were recurrently observed in late summer, when faeces contributed up to 100% of organic carbon. Unusually high fluxes were recorded in winter 1995, when faecal pellets accounted for 84.6% of the organic carbon. Peak fluxes were always driven by the sinking of faecal pellets, that hence appear to be the most efficient vector of export in the polynya of Terra Nova Bay. A major flux component was the pteropod Limacina helicina, which repeatedly sank in high amounts after the growing season. In April–June, L. helicina probably transported biogenic carbon to deep layers as a passive sinker. The inclusion of pteropods in flux estimates resulted in values that were up to 20 (for total mass), 25 (for organic matter) and 48 (for carbonate) times higher than the previously measured fluxes. Fluxes are known to be biased by swimmers, but ultimately attention must be paid to a possible erroneous categorization of some zooplankton as swimmers to avoid severe underestimation of fluxes of total mass (up to 95% in our study), organic matter (up to 96%) and carbonate (up to 100%).