Theoretical and experimental SERS study of thiocarbonyl compounds adsorbed on metal nanoparticles

Thiocarbonyl compounds have been reported to exhibit interesting biological and pharmacological properties but they are many often characterized by their toxicological effects. However the chemistry of thiobenzoic acid (TBA) and thiobenzamide (TB) has not been fully studied yet. Some of the biological studies of TBA are related to the tautomerism of thiocarboxylic acids and the important role that the -C(=O)-S and -C(=S)-O functional groups play in the catalytic activities of enzymes such as cysteine or serine proteases.1 From a chemical point of view, thiocarboxylates are an interesting type of molecules having two different donor atoms, a soft sulfur donor atom and a hard oxygen donor one. The presence of these unlike groups can lead to the bonding with metal surfaces. Likewise the interaction of thiobenzamide and their derivatives with metals is of great interest because both the sulfur and nitrogen atoms are also able to coordinate with the surface. Therefore the high affinity of these molecules for metal surfaces makes them suitable SERS target adsorbates. Taking advantage of the fact that SERS spectroscopy is both surface selective and highly sensitive we have attempted to determine the molecular structure of TBA and TB once they are adsorbed on the metal. The main objective of this work is focussed on discussing the observed vibrational wavenumber shifts of TBA and TB upon adsorption on silver nanoparticles. In this work the SERS substrates have been prepared by using different colloidal silver solutions according to the method described by Creighton et al.2 and Leopold and Lendl.3 The analysis of the vibrational wavenumbers shifts of the Raman and SERS spectra allow us to know the adsorption process (Figure 1). In the case of TBA, the wavenumber of the SERS band assigned to (C=O) vibrational mode shows an important blue shift up to 40 cm-1 with respect to the Raman whereas the (C-S) band undergoes a red shift up to 40 cm-1. These results suggest a unidentate coordination of TBA to the silver surface through the sulfur atom. On the other hand, the SERS band assigned in the case of TB to Amide III (mainly (CN)) exhibits a significant blueshift up to 41 cm-1, and the SERS band assigned to Amide I (mainly (CS)) shows a red shift up to 11 cm-1. These wavenumber shifts indicate that TB interacts to the silver surface through the sulfur atom. Interestingly, in previous SERS studies of pyridinecarboxamides and benzamide we have observed that some SERS bands assigned to 1;ring, Amide I (mainly (C=O)) and Amide III (mainly C-N)) show wavenumber shifts of +50, -50 and +10 cm-1, respectively, which were attributed to the deprotonation of carboxamide group.4,5 Finally, in order to verify experimental results DFT calculations have been carried out for different silver complexes of TBA and TB concluding that the unidentate coordination is the most likely interaction of both of them.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Chemical abundances of damped Lyman alpha systems in the XQ-100 survey

The XQ-100 survey has provided high signal-noise spectra of 100 redshift 3-4.5 quasars with the X-Shooter spectrograph. The metal abundances for 13 elements in the 41 damped Lyman alpha systems (DLAs) identified in the XQ-100 sample are presented, and an investigation into abundances of a variety of DLA classes is conducted. The XQ-100 DLA sample contains five DLAs within 5000 km/s of their host quasar (proximate DLAs; PDLAs) as well as three sightlines which contain two DLAs within 10,000 km/s of each other along the same line-of-sight (multiple DLAs; MDLAs). Combined with previous observations in the literature, we demonstrate that PDLAs with logN(HI)<21.0 show lower [S/H] and [Fe/H] (relative to intervening systems with similar redshift and N(HI)), whilst higher [S/H] and [Si/H] are seen in PDLAs with logN(HI)>21.0. These abundance discrepancies are independent of their line-of-sight velocity separation from the host quasar, and the velocity width of the metal lines (v90). Contrary to previous studies, MDLAs show no difference in [alpha/Fe] relative to single DLAs matched in metallicity and redshift. In addition, we present follow-up UVES data of J0034+1639, a sightline containing three DLAs, including a metal-poor DLA with [Fe/H]=-2.82 (the third lowest [Fe/H] in DLAs identified to date) at z=4.25. Lastly we study the dust-corrected [Zn/Fe], emphasizing that near-IR coverage of X-Shooter provides unprecedented access to MgII, CaII and TiII lines (at redshifts 3-4) to provide additional evidence for subsolar [Zn/Fe] ratio in DLAs.Comment: Accepted to MNRAS. 19 pages plus Appendix material (102 pages total

Near-Infrared Polarimetric Adaptive Optics Observations of NGC 1068: A torus created by a hydromagnetic outflow wind

We present J' and K' imaging linear polarimetric adaptive optics observations of NGC 1068 using MMT-Pol on the 6.5-m MMT. These observations allow us to study the torus from a magnetohydrodynamical (MHD) framework. In a 0.5" (30 pc) aperture at K', we find that polarisation arising from the passage of radiation from the inner edge of the torus through magnetically aligned dust grains in the clumps is the dominant polarisation mechanism, with an intrinsic polarisation of 7.0%$\pm$2.2%. This result yields a torus magnetic field strength in the range of 4$-$82 mG through paramagnetic alignment, and 139$^{+11}_{-20}$ mG through the Chandrasekhar-Fermi method. The measured position angle (P.A.) of polarisation at K$'$ is found to be similar to the P.A. of the obscuring dusty component at few parsec scales using infrared interferometric techniques. We show that the constant component of the magnetic field is responsible for the alignment of the dust grains, and aligned with the torus axis onto the plane of the sky. Adopting this magnetic field configuration and the physical conditions of the clumps in the MHD outflow wind model, we estimate a mass outflow rate $\le$0.17 M$_{\odot}$ yr$^{-1}$ at 0.4 pc from the central engine for those clumps showing near-infrared dichroism. The models used were able to create the torus in a timescale of $\geq$10$^{5}$ yr with a rotational velocity of $\leq$1228 km s$^{-1}$ at 0.4 pc. We conclude that the evolution, morphology and kinematics of the torus in NGC 1068 can be explained within a MHD framework.Comment: 14 pages, 4 figures, Accepted by MNRA

Current research into brain barriers and the delivery of therapeutics for neurological diseases: a report on CNS barrier congress London, UK, 2017.

This is a report on the CNS barrier congress held in London, UK, March 22-23rd 2017 and sponsored by Kisaco Research Ltd. The two 1-day sessions were chaired by John Greenwood and Margareta Hammarlund-Udenaes, respectively, and each session ended with a discussion led by the chair. Speakers consisted of invited academic researchers studying the brain barriers in relation to neurological diseases and industry researchers studying new methods to deliver therapeutics to treat neurological diseases. We include here brief reports from the speakers

CD69 is a TGF-β/1α,25-dihydroxyvitamin D3 target gene in monocytes

CD69 is a transmembrane lectin that can be expressed on most hematopoietic cells. In monocytes, it has been functionally linked to the 5-lipoxygenase pathway in which the leukotrienes, a class of highly potent inflammatory mediators, are produced. However, regarding CD69 gene expression and its regulatory mechanisms in monocytes, only scarce data are available. Here, we report that CD69 mRNA expression, analogous to that of 5-lipoxygenase, is induced by the physiologic stimuli transforming growth factor-β (TGF-β) and 1α,25-dihydroxyvitamin D3 (1α,25(OH)2D3) in monocytic cells. Comparison with T- and B-cell lines showed that the effect was specific for monocytes. CD69 expression levels were increased in a concentration-dependent manner, and kinetic analysis revealed a rapid onset of mRNA expression, indicating that CD69 is a primary TGF-β/1α,25(OH)2D3 target gene. PCR analysis of different regions of the CD69 mRNA revealed that de novo transcription was initiated and proximal and distal parts were induced concomitantly. In common with 5-lipoxygenase, no activation of 0.7 kb or ~2.3 kb promoter fragments by TGF-β and 1α,25(OH)2D3 could be observed in transient reporter assays for CD69. Analysis of mRNA stability using a transcription inhibitor and a 3′UTR reporter construct showed that TGF-β and 1α,25(OH)2D3 do not influence CD69 mRNA stability. Functional knockdown of Smad3 clearly demonstrated that upregulation of CD69 mRNA, in contrast to 5-LO, depends on Smad3. Comparative studies with different inhibitors for mitogen activated protein kinases (MAPKs) revealed that MAPK signalling is involved in CD69 gene regulation, whereas 5-lipoxygenase gene expression was only partly affected. Mechanistically, we found evidence that CD69 gene upregulation depends on TAK1-mediated p38 activation. In summary, our data indicate that CD69 gene expression, conforming with 5-lipoxygenase, is regulated monocyte-specifically by the physiologic stimuli TGF-β and 1α,25(OH)2D3 on mRNA level, although different mechanisms account for the upregulation of each gene

Latest developments in data analysis tools for disruption prediction and for the exploration of multimachine operational spaces.

In the last years significant efforts have been devoted to the development of advanced data analysis tools to both predict the occurrence of disruptions and to investigate the operational spaces of devices, with the long term goal of advancing the understanding of the physics of these events and to prepare for ITER. On JET the latest generation of the disruption predictor called APODIS has been deployed in the real time network during the last campaigns with the new metallic wall. Even if it was trained only with discharges with the carbon wall, it has reached very good performance, with both missed alarms and false alarms in the order of a few percent (and strategies to improve the performance have already been identified). Since for the optimisation of the mitigation measures, predicting also the type of disruption is considered to be also very important, a new clustering method, based on the geodesic distance on a probabilistic manifold, has been developed. This technique allows automatic classification of an incoming disruption with a success rate of better than 85%. Various other manifold learning tools, particularly Principal Component Analysis and Self Organised Maps, are also producing very interesting results in the comparative analysis of JET and ASDEX Upgrade (AUG) operational spaces, on the route to developing predictors capable of extrapolating from one device to another

Inverse Association between Dietary Iron Intake and Gastric Cancer: A Pooled Analysis of Case‐Control Studies of the Stop Consortium

Background: Inconsistent findings have been reported regarding the relationship between dietary iron intake and the risk of gastric cancer (GC). Methods: We pooled data from 11 case‐control studies from the Stomach Cancer Pooling (StoP) Project. Total dietary iron intake was derived from food frequency questionnaires combined with national nutritional tables. We derived the odds ratios (ORs) and 95% confidence intervals (CIs) for quartiles of dietary iron through multivariable unconditional logistic regression models. Secondary analyses stratified by sex, smoking status, caloric intake, anatomical subsite and histological type were performed. Results: Among 4658 cases and 12247 controls, dietary iron intake was inversely associated with GC (per quartile OR 0.88; 95% CI: 0.83–0.93). Results were similar between cardia (OR = 0.85, 95% CI = 0.77–0.94) and non‐cardia GC (OR = 0.87, 95% CI = 0.81–0.94), and for diffuse (OR = 0.79, 95% CI = 0.69–0.89) and intestinal type (OR = 0.88, 95% CI = 0.79–0.98). Iron intake exerted an independent effect from that of smoking and salt intake. Additional adjustment by meat and fruit/vegetable intake did not alter the results. Conclusions: Dietary iron is inversely related to GC, with no difference by subsite or histological type. While the results should be interpreted with caution, they provide evidence against a direct effect of iron in gastric carcinogenesis

Vector field as a quintessence partner

We derive generic equations for a vector field driving the evolution of flat homogeneous isotropic universe and give a comparison with a scalar filed dynamics in the cosmology. Two exact solutions are shown as examples, which can serve to describe an inflation and a slow falling down of dynamical ``cosmological constant'' like it is given by the scalar quintessence. An attractive feature of vector field description is a generation of ``induced mass'' proportional to a Hubble constant, which results in a dynamical suppression of actual cosmological constant during the evolution.Comment: 14 pages, LaTeX file, iopart class, discussion extended, reference adde