Selective reagents in chemical ionization mass spectrometry: Tetramethylsilane with ethers

Chemical ionization mass spectra of several ethers obtained with He/(CH₃)₄Si mixtures as the reagent gases contain abundant [M + 73]⁺ adduct ions which identify the relative molecular mass. For the di-n-alkyl ethers, these [M + 73]⁺ ions are formed by sample ion/sample molecule reactions of the fragment ions, [M + 73 ? C_nH_2n]⁺ and [M + 73 ? 2CnH_2n]⁺. Small amounts of [M + H]⁺ ions are also formed, predominantly by proton transfer reactions of the [M + 73 ? 2CnH_2n]⁺ or [(CH₃)₃SiOH₂]⁺ ions with the ethers. The di-s-alkyl ethers give no [M + 73] ⁺ ions, but do give [M + H]⁺ ions, which allow the determination of the relative molecular mass. These [M + H]⁺ ions result primarily from proton transfer reactions from the dominant fragment ion, [(CH₃)₃SiOH₂]⁺ with the ether. Methyl phenyl ether gives only [M + 73]⁺ adduct ions, by a bimolecular addition of the trimethylsilyl ion to the ether, not by the two-step process found for the di-n-alkyl ethers. Ethyl phenyl ether gives [M + 73]⁺ by both the two-step process and the bimolecular addition. Although the mass spectra of the alkyl etherr are temperature-dependent, the sensitivities of the di-alkyl ethers and ethyl phenyl ether are independent of temperature. However, the sensitivity for methyl phenyl ether decreases significantly with increasing temperature.     

Synthesis and characterisation of estrogenic carriers for cytotoxic Pt(II) fragments: biological activity of the resulting complexes

This paper describes the synthesis and the spectroscopic characterisation of cis-dichloro[N-(4-(17alpha-ethynylestradiolyl)-benzyl)-ethylenediamine]platinum(II) and cis-diamino[2-(4-(17alpha-ethynylestradiolyl)-benzoylamino)-malonato]platinum(II). These complexes were synthesised in good yield according to multi-step procedures based on the classical and non-classical Sonogashira coupling reaction, respectively. These compounds retain an acceptable degree of relative binding affinity (RBA) for the alpha form of estrogen receptor. Combined treatment of breast cancer cell lines, namely hormone-sensitive MCF-7 and hormone-insensitive MDA-MB-231 cell lines, indicates that these compounds maintain agonistic activity so that the potential advantage in vehiculation of the cytotoxic moiety by means of the receptor system is counteracted by the proliferative effect of the estrogenic component of the entire molecule, especially at low concentrations.     

N‐Linked Glycans of Chloroviruses Sharing a Core Architecture without Precedent

N‐glycosylation is a fundamental modification of proteins and exists in the three domains of life and in some viruses, including the chloroviruses, for which a new type of core N‐glycan is herein described. This N‐glycan core structure, common to all chloroviruses, is a pentasaccharide with a β‐glucose linked to an asparagine residue which is not located in the typical sequon N‐X‐T/S. The glucose is linked to a terminal xylose unit and a hyperbranched fucose, which is in turn substituted with a terminal galactose and a second xylose residue. The third position of the fucose unit is always linked to a rhamnose, which is a semiconserved element because its absolute configuration is virus‐dependent. Additional decorations occur on this core N‐glycan and represent a molecular signature for each chlorovirus.     

Monotonicity,continuity and differentiability results for the Lp Hardy constant

We consider the L^p Hardy inequality involving the distance to the boundary for a domain in the n-dimensional Euclidean space. We study the dependence on p of the corresponding best constant and we prove monotonicity, continuity and differentiability results. The focus is on non-convex domains in which case such a constant is in general not explicitly known.     

Rawlsian altruism with perfect discrimination leads to social efficiency

Recent studies draw attention on the highly specialized capacity of human beings in recognizing altruists versus cheaters in social interactions. These results hint at the existence of specialized abilities that support discriminating behavior in strategic interactions. In this paper, we explore the implications of discriminating behavior in the study of the indirect evolutionary selection of selfish versus altruistic motivations in the context of generic 2×2 base games, and in particular for coordination and cooperation scenarios. We find that inequality averse (Rawlsian) altruism can enforce under rather general conditions socially optimal outcomes, including cases where selfishness cannot, such as in prisoner’s dilemmas. Inequality seeking (Nietzschian) altruism in no case improves upon Rawlsian altruism in terms of social optimality of outcomes, and often does worse. In the cooperation scenario in particular, Nietzschean altruism never manages to implement the cooperative outcome. Under perfect discrimination, moreover, inequality averse (Rawlsian) altruism often evolves at the expense of selfishness. These results suggest that the development of sophisticated discrimination abilities may be strongly adaptive in supporting fairness-oriented forms of pro-sociality in humans in the context of social dilemmas and coordination problems.     

PIXE‐alpha non‐destructive and in situ compositional investigation of black gloss on ancient pottery

The chemical characterization of the black gloss on ancient pottery is, since several years, the object of different scientific investigations. Among the different typologies of black gloss, the Attic one is the most refined, because it is prepared by using a fine suspension of an illitic clay applied on the surface of the clay body so that, after an oxiding‐reducing‐oxiding firing cycle at high temperature (800–950 °C), it reaches the typical shiny black aspect. Red figure vases were largely produced in South Italy often reaching a high artistic level. This is the case of the Sicilian red figure vases, sometimes called ‘Sicelioti’, whose production began in Sicily around the end of the fifth century BC and continued until the beginning of the third century BC . The aim of this work is to submit and compare a selection of data related to the chemical composition of the surface black gloss of some Attic and Sicilian red figure vases: This has been investigated, and a chemical‐based discrimination has been proposed. The non‐destructive particle‐induced X‐ray emission‐alpha portable spectrometer was used. The results, carried out in situ at the ‘Paolo Orsi’ Archaeological Museum in Syracuse (Sicily), together with the ones recently obtained in similar analyses at the Archaeological Museum of Catania University, confirmed the compositional stability of Attic vase black gloss and indicated that in a well‐defined time period, the chemical composition of the Sicilian black gloss decorations is very stable and superimposable with that of the contemporary Attic artifacts. Copyright © 2016 John Wiley & Sons, Ltd.     

QSAR Models for Human Carcinogenicity: An Assessment Based on Oral and Inhalation Slope Factors

Carcinogenicity is a crucial endpoint for the safety assessment of chemicals and products. During the last few decades, the development of quantitative structure–activity relationship ((Q)SAR) models has gained importance for regulatory use, in combination with in vitro testing or expert-based reasoning. Several classification models can now predict both human and rat carcinogenicity, but there are few models to quantitatively assess carcinogenicity in humans. To our knowledge, slope factor (SF), a parameter describing carcinogenicity potential used especially for human risk assessment of contaminated sites, has never been modeled for both inhalation and oral exposures. In this study, we developed classification and regression models for inhalation and oral SFs using data from the Risk Assessment Information System (RAIS) and different machine learning approaches. The models performed well in classification, with accuracies for the external set of 0.76 and 0.74 for oral and inhalation exposure, respectively, and r² values of 0.57 and 0.65 in the regression models for oral and inhalation SFs in external validation. These models might therefore support regulators in (de)prioritizing substances for regulatory action and in weighing evidence in the context of chemical safety assessments. Moreover, these models are implemented on the VEGA platform and are now freely downloadable online.     

Mentha pulegium L.: A Plant Underestimated for Its Toxicity to Be Recovered from the Perspective of the Circular Economy

The aim of the study was to investigate the micromorphology of Mentha pulegium leaves and flowers harvested in three different Sicilian (Italy) areas with peculiar pedo-climatic conditions, and to characterize the phytochemical profile, the phytotoxic activity, and the eco-compatibility of their essential oils (EOs) for potential use as safe bioherbicides. Light microscopy (LM) and scanning electron microscopy (SEM) highlighted that M. pulegium indumentum consists of non-glandular and glandular trichomes of different types. Peltate trichomes of plants from the different sites showed few significant differences in dimension and abundance, but they were characterized by a surprisingly high number of secretory cells both in leaves and flowers. Phytochemical analyses showed that oxygenated monoterpenes were the most abundant class in all the EOs investigated (92.2–97.7%), but two different chemotypes, pulegone/isomenthone and piperitone/isomenthone, were found. The complex of morphological and phytochemical data indicates that soil salinity strongly affects the expression of the toxic metabolite pulegone, rather than the EO yield. Phytotoxicity tests showed a moderate activity of EOs against the selected species as confirmed by α-amylase assay. Moreover, the low toxicity on brine shrimp provided a rationale for the possible use of investigated EOs as eco-friendly herbicides.