Decomposition of protonated noradrenaline and normetanephrine assisted by NH2 migration studied by electrospray tandem mass spectrometry and molecular orbital calculations

As part of a research program on neurotransmitters in a biological fluid, the fragmentations characterising catecholamines protonated under electrospray ionisation (ESI) conditions, under low collision energy in a triple-quadrupole mass spectrometer, were investigated. The decompositions of protonated noradrenaline (VH) and normetanephrine (VIH) were studied. Both precursor ions eliminate first H2O at very low collision energy, and the fragmentations of [MH-H2O]+ occur at higher collision energy. The breakdown graphs of [MH-H2O]+ ions, with collision energy varying from 0-40 eV in the laboratory frame, are presented. [VIH-H2O]+ ions lose competitively NH3 and CH3OH. For [VH-H2O]+ the loss of NH3 is dominant while H2O is eliminated at very low abundance at all collision energies. All of these secondary fragmentations are followed at higher collision energies by elimination of CO. These fragmentations are interpreted by means of ab initio calculations up to the B3LYP/6-311+G(2d,2p) level of theory. The elimination of H2O requires first the isomerisation of N-protonated forms, chosen as energy references, to O-protonated forms. The isomerisation barriers are calculated to be lower than 81 kJ/mol above the N-protonated forms. The elimination of NH3 from [MH-H2O]+ requires first the migration, via a cyclisation, of the amine function from the linear chain to the aromatic ring in order to prevent the formation of unstable disubstituted carbocations in the ring. The barriers associated with the loss of NH3 are located 220 and 233 kJ/mol above VH and 219 kJ/mol above VIH. The energy barrier for the loss of ROH is located 236 and 228 kJ/mol above VH and VIH, respectively. The absence of ions corresponding to [VH-2H2O]+ is due to a parasitic mechanism with an activation barrier lower than 236 kJ/mol that leads to a stable species unable to fragment, thus preventing the second loss of H2O. Losses of CO following the secondary fragmentations involve activation barriers higher than 330 kJ/mol.     

Polysaccharide‐block‐polypeptide Copolymer Vesicles: Towards Synthetic Viral Capsids

Natural inspiration : Amphiphilic polysaccharide‐block‐polypeptide copolymers were synthesized by click chemistry from dextran end‐functionalized with an alkyne group and poly(γ‐benzyl L ‐glutamate) end‐functionalized with an azide group. The ability of these copolymers to self‐assemble into small vesicles (see picture) suggests the possibility of a new generation of drug‐ and gene‐delivery systems whose structure mimics that of viruses.

     

Solid-phase extraction of triazole fungicides from water samples using disks impregnated with carbon nanotubes followed by GC-MS analysis

Triazole fungicides are pesticides widely employed in the cultivation of fruits, vegetables and grains. However, their ability to change the steroid hormone biosynthesis may result in endocrine complications for mammals, as well as changes in cholesterol and triglyceride levels and hepatotoxicity. The analysis of the triazole fungicides in superficial waters is important in order to monitor the risk for the biota. However, the use of efficient extraction procedures has been necessary in order to concentrate these pesticides before the analysis. In-disk solid-phase extraction (SPE) can be highlighted as a potential pre-concentration technique, mainly because the possibility to extract the analytes from a large sample volume, increasing the method detectability. Carbon nanotubes (CNTs) have been often used as solid extraction phase due to their high sorption capacity, surface area and internal volume, as well as mechanical, chemical and thermal stability. In this paper, we proposed the preparation of a new SPE disk impregnated with CNTs for the extraction of triazole fungicides from environmental water samples. The disks were obtained by acid corrosion of a cellulose membrane followed by its impregnation with CNTs. The developed method was validated for the analysis of triadimenol, tebuconazole and epoxiconazole, according to international validation protocols. The limits of quantification obtained for triadimenol, tebuconazole and epoxiconazole were 0.1, 0.1 and 0.05 µg L^?1, respectively. The linearity ranged from 0.05 to 10.00 µg L^?1 for epoxiconazole and from 0.1 to 10.00 µg L^?1 for triadimenol and tebuconazole, with correlation coefficients higher than 0.999 for all of them. The precisions, expressed as relative standard deviation, were lower than 12%. The accuracies were within ?12.07% to 17.7% (expressed as relative error).     

Synthesis,structure and properties of N-aminosaccharin – A selective inhibitor of human carbonic anhydrase I

Previously unknown N-aminosaccharin was prepared in good yield via the one-step direct amination of saccharin sodium salt with hydroxylamine-O-mesitylenesulfonic acid (MSH) and its reactivity investigated. N-aminosaccharin and its derivatives were tested against hCA isoforms and the parent compound was identified to be a selective, low micromolar inhibitor (K_i = 8.8 μM) of hCA I. These findings provide a ligand-efficient starting point for the design of potent hCA I inhibitors – a promising drug target for retinal/cerebral edema treatment.     

Dual input–output pairs for modeling hysteresis inspired by mem-models

We call attention to a dual-pair concept for modeling hysteresis involving instantaneous switching: Specifically, there are two input–output pairs for each hysteresis model under one specific input, namely a differential pair and an integral pair. Currently in engineering mechanics, only one pair is being recognized and utilized, not the other. Whereas this dual-pair concept is inherent in the differential and algebraic forms of memristors and memcapacitors, the concept has not been carried over to memristive system theory, nor to memcapacitive system theory. We show that the “zero-crossing” feature in memristors, memcapacitors, and memristive/memcapacitive models (i.e., the “mem-models”) is also a feature of the differential pairs of well-known non-mem-models, examples of which are Ramberg–Osgood, Bouc–Wen, bilinear hysteresis, and classical Preisach. The dual-pair concept thus connects mem-models and non-mem-models, thereby facilitating the modeling of hysteresis, and raising a set of scientific questions for further studies that might not otherwise come to awareness.     

A novel approach for strong S-Box generation algorithm design based on chaotic scaled Zhongtang system

Nonlinear Dynamics - Substitution Box (S-Box) is one of the most significant structures used to create an encryption which is strong and resistant against attacks in block encryption algorithms....     

Uranium-bearing francolites present in organic-rich limestones of NW Greece: a preliminary study using synchrotron radiation and fission track techniques

Synchrotron radiation techniques (μ-XRF and μ-XANES) were applied to the study of organic-rich phosphatized limestones of NW Greece (Epirus). The results revealed uranium accumulation in areas of the material containing, among others, carbonate apatite (francolite) and organic matter. The UL ₃-edge of μ-XANES spectra showed that uranium was present in tetravalent form. U-bearing francolite crystals were separated from the rock and characterized by Raman spectroscopy and microprobe. The analysis of the crystals also indicated the presence of sodium and sulfur. The uranium presence in the crystals was also visualized, after neutron irradiation and etching, by the observation of the fission tracks.

     

Designing liquid-crystalline dendronised hexa-adducts of [60]fullerene via click chemistry

ABSTRACT

Liquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C₆₀) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, ¹H and ¹³C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C₆₀ functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C₆₀ decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C₆₀ is a unique synthetic platform for the design of fullerodendrimers and dendronised materials.