Sediment metal contamination in a creek flowing from a pristine to an industrial area of Trieste Province (Italy)

The following metals: Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined by inductively coupled plasma - atomic emission spectroscopy (ICP-AES) in fluvial sediments of Rosandra Creek, using two different, strong and mild sediment decomposition methods. The purpose was to obtain information about the contamination by metals and distribution paths of pollutants in the area crossed by Rosandra Creek: this little river is the unique epigeous watercourse in the Italian Karst and very few data can be found in literature. In this area, we can find a natural park, but also agricultural activities and an industrial district that was recently defined as "polluted site of national interest". By comparing the results of the strong and mild extraction we have obtained the percentage of extraction and enrichment factors for each metal in the different sediments of the sites R2 and R3 exposed to pollution, while the site R1 was considered as a pristine one because situated in the natural park. The computed enrichment factors are generally not very high, but copper, lead and zinc have factors that require attention. The principal component analysis (PCA) shows that the typically anthropogenic metals (as Cr, Pb, Cu and Zn) constitute the first factor, while the lithogenic metals, as Fe and Ni, constitute the second one; moreover the score plots permit to classify and distinguish the 3 sites: site R3, possibly the more exposed to contamination, has high scores both for anthropogenic and lithogenic metals.     

Sulphur speciation of PM10 samples by XANES spectroscopy

Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to identify sulphur compounds in PM10 samples collected simultaneously at two sites with different environmental situations in the province of Trieste (NE of Italy), during summer and winter seasons respectively. The first site is an industrial site located near a steel mill plant and the second is a coastal site. The sulphur speciation at the industrial site has shown the presence of the following sulphur compounds in both seasons: organic compounds (thiophenes or Polycyclic Aromatic Sulphur Heterocycles — PAHs) and sulphates while in the winter season sulphites were also present. In the coastal site organic compounds (thiophenes or PASHs) and sulphate were found during winter season, moreover bisulphates were found during summer season. Relative percentages of the different sulphur compounds have shown that sulphate is the most abundant form of sulphur in the industrial site samples during both seasons and in the coastal site sample collected during the winter season (> 98%); in the coastal site sample collected during the summer season the relative percentages of bisulphate and sulphate were around 40% and 60% respectively.      

Synthesis of Octyl β-D-Glucopyranoside-aminobutyric (GABA) and Aminohydroxybutyric (GABOB) Conjugates

Abstract

The syntheses of octyl β-D-glucopyranoside-GABA and GABOB conjugates are presented. The selectively protected octyl-β-D-glucopyranoside and γ-aminobutyric acids were coupled with N, N'-dicyclohexylcarbodiimide. ¹H and ¹³C NMR spectroscopy were used to verify the proposed structures.     

Smoothing of rational m-ropes

In a recent paper, Gallego, González and Purnaprajna showed that rational 3-ropes can be smoothed. We generalise their proof, and obtain smoothability of rational m-ropes for m ≥ 3.     

Radical defects modulate the photocatalytic response in 2D-graphitic carbon nitride

Graphitic carbon nitride (gCN) is an important heterogeneous metal-free catalytic material. Thermally induced post-synthetic modifications, such as amorphization and/or reduction, were recently used to enhance the photocatalytic response of these materials for certain classes of organic transformations, with structural defects possibly playing an important role. The knowledge of how these surface modifications modulate the photocatalytic response of gCN is therefore not only interesting from a fundamental point of view, but also necessary for the development and/or tuning of metal-free gCN systems with superior photo-catalytic properties. Herein, employing density functional theory calculations and combining both the periodic and molecular approaches, in conjunction with experimental EPR measurements, we demonstrate that different structural defects on the gCN surface generate distinctive radical defect states localized within the electronic bandgap, with only those correlated with amorphous and reduced gCN structures being photo-active. To this end, we (i) model defective gCN surfaces containing radical defect states; (ii) assess the interactions of these defects with the radical precursors involved in the photo-driven alkylation of electron-rich aromatic compounds (namely perfluoroalkyl iodides); and (iii) describe the photo-chemical processes triggering the initial step of that reaction at the gCN surface. We provide a coherent structure/photo-catalytic property relationship on defective gCN surfaces, elaborating how only specific defect types act as binding sites for the perfluoroalkyl iodide reagent and can favor a photo-induced charge transfer from the gCN surface to the molecule, thus triggering the perfluoroalkylation reaction.

The nature of radical defects governs the photocatalytic activity of graphitic carbon nitride.     

Dinuclear gold(I) Complexes with Bidentate NHC Ligands as Precursors for Alkynyl Complexes via Mechanochemistry

The use of alkynyl gold(I) complexes covers different research fields, such as bioinorganic chemistry, catalysis, and material science, considering the luminescent properties of the complexes. Regarding this last application, we report here the synthesis of three novel dinuclear gold(I) complexes of the general formula [(diNHC)(Au-C≡CPh)₂]: two Au-C≡CPh units are connected by a bridging di(N-heterocyclic carbene) ligand, which should favor the establishment of semi-supported aurophilic interactions. The complexes can be easily synthesized through mechanochemistry upon reacting the pristine dibromido complexes [(diNHC)(AuBr)₂] with phenylacetylene and KOH. Interestingly, we were also able to isolate the monosubstituted complex [(diNHC)(Au-C≡CPh)(AuBr)]. The gold(I) species were fully characterized by multinuclear NMR spectroscopy and mass spectrometry. The emission properties were also evaluated, and the salient data are comparable to those of analogous compounds reported in the literature.     

Privacy-Preserving Design of Scalar LQG Control

This paper studies the agent identity privacy problem in the scalar linear quadratic Gaussian (LQG) control system. The agent identity is a binary hypothesis: Agent A or Agent B. An eavesdropper is assumed to make a hypothesis testing the agent identity based on the intercepted environment state sequence. The privacy risk is measured by the Kullback–Leibler divergence between the probability distributions of state sequences under two hypotheses. By taking into account both the accumulative control reward and privacy risk, an optimization problem of the policy of Agent B is formulated. This paper shows that the optimal deterministic privacy-preserving LQG policy of Agent B is a linear mapping. A sufficient condition is given to guarantee that the optimal deterministic privacy-preserving policy is time-invariant in the asymptotic regime. It is also shown that adding an independent Gaussian random process noise to the linear mapping of the optimal deterministic privacy-preserving policy cannot improve the performance of Agent B. The numerical experiments justify the theoretic results and illustrate the reward–privacy trade-off.     

Adsorption of multivalent alkylthiols on Au(111) surface: Insights from DFT

The adsorption of multivalent thiols on gold (111) surface was investigated using density functional theory applying the Perdew–Burke–Ernzerhof functional. Through the comparison of differences in energetics, structure and charge density distribution of a set of monodentate and polydentate thiols, we have described in detail the factors affecting the adsorption energy and the role played by the multivalence, which causes a decreasing of adsorption energy because of both electronic and steric hindrance effects. Finally, the comparison between the adsorption of 1,2‐ and 1,3‐disulfides revealed how the chain length may affect the cleavage of the S? S bond when they adsorb on Au(111) surface. © 2013 Wiley Periodicals, Inc.     

Sets Computing the Symmetric Tensor Rank

Let ${\nu_{d} : \mathbb{P}^{r} \rightarrow \mathbb{P}^{N}, N := \left( \begin{array}{ll} r + d \\ \,\,\,\,\,\, r \end{array} \right)- 1,}$ denote the degree d Veronese embedding of ${\mathbb{P}^{r}}$ . For any ${P\, \in \, \mathbb{P}^{N}}$ , the symmetric tensor rank sr(P) is the minimal cardinality of a set ${\mathcal{S} \subset \nu_{d}(\mathbb{P}^{r})}$ spanning P. Let ${\mathcal{S}(P)}$ be the set of all ${A \subset \mathbb{P}^{r}}$ such that ${\nu_{d}(A)}$ computes sr(P). Here we classify all ${P \,\in\, \mathbb{P}^{n}}$ such that sr(P) <  3d/2 and sr(P) is computed by at least two subsets of ${\nu_{d}(\mathbb{P}^{r})}$ . For such tensors ${P\, \in\, \mathbb{P}^{N}}$ , we prove that ${\mathcal{S}(P)}$ has no isolated points.