Dispersive micro-solid phase extraction of 16 priority polycyclic aromatic hydrocarbons from water by using thermally treated clinoptilolite,and their quantification by GC-MS

The authors report on a novel sorbent (thermally treated natural zeolite; clinoptilolite) for use in dispersive micro-solid phase extraction (D-μ-SPE) of polycyclic aromatic hydrocarbons (PAHs) from water samples. The method was applied to the D-μ-SPE of 16 priority PAHs which then were quantified by gas chromatography with mass spectrometric detection (GC-MS). The method was validated in terms of specificity and selectivity, linearity and linear range, accuracy, precision, uncertainty, limits of detection and quantification. Figures of merit include (a) linear analytical ranges between 2.08 and 208 ppb, and (b) detection limits in the range from 0.01 to 0.92 ppb. The method was successfully applied to the determination of PAHs in river waters.

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Graphical abstract Schematic representation of dispersive micro-solid phase extraction (D-μ-SPE) of trace levels of PAHs in water samples by using thermally treated clinoptilolite as sorbent prior to gas chromatography-mass spectrometry analysis (GC-MS).

     

C–H⋅<Emphasis Type="Italic">s</Emphasis>O hydrogen bond networks in <Emphasis Type="Italic">E</Emphasis>- and Z-unsaturated esters of C-glycosides

Methyl E(Z)-4,7 anhydro-5-benzamido-6,8-di-O-benzoyl-2,3,5-trideoxy-d-allo-oct-2-enoate have been synthesized like intermediates and isolated as single crystals during the synthesis of pyrazole-related C nucleosides as synthetic product with cytotoxic activity.¹ Crystal structures of E(Z) isomers were determined by X-ray analysis. E isomer crystallizes in the triclinic crystal system, space group P1, a = 5.319(1) Å, b = 10.758(2) Å, c = 12.229(2) Å, α = 72.38(2)^∘, β = 89.97(2)^∘, γ = 87.07(2)^∘, D_x = 1.320 Mgm⁻³ and Z isomer in the orthorhombic crystal system, space group P2₁2₁2₁, a = 5.1297(13) Å, b = 19.667(5) Å, c = 25.871(6) Å, D_x = 1.348 Mgm⁻³. The molecular structure was solved by direct method on the basis of 2609 and 2727 unique reflections recorded at the temperature 293 K (E-isomer) and 173 K (Z-isomer) up to the final R-factor 0.0378 and 0.0435, respectively. C–H⋅sO contact networks were analyzed and the correlation established between the existence of the weak C–H⋅sO hydrogen bonds and the melting point of the single crystals.     

The Square of Opposition and the Four Fundamental Choices

Each predicate of the Aristotelian square of opposition includes the word “is”. Through a twofold interpretation of this word the square includes both classical logic and non-classical logic. All theses embodied by the square of opposition are preserved by the new interpretation, except for contradictories, which are substituted by incommensurabilities. Indeed, the new interpretation of the square of opposition concerns the relationships among entire theories, each represented by means of a characteristic predicate. A generalization of the square of opposition is achieved by not adjoining, according to two Leibniz’ suggestions about human mind, one more choice about the kind of infinity; i.e., a choice which was unknown by Greek’s culture, but which played a decisive role for the birth and then the development of modern science. This essential innovation of modern scientific culture explains why in modern times the Aristotelian square of opposition was disregarded. This work was completed with the support of our -pert.     

Spectral signatures and molecular origin of acid dissociation intermediates

The existence of a broad, mid-infrared absorption ranging from 1000 to 3000 cm(-1) is usually interpreted as a signature for the existence of protonated water networks. Herein, we use cryogenic mixtures of water and hydrogen fluoride (HF) and show experimental and computational evidence that similarly wide absorptions can be generated by a broad distribution of proton-shared and ion pair complexes. In the present case, we demonstrate that the broadening is mainly inhomogeneous, reflecting the fact that the topology of the first solvation shell determines the local degree of ionization and the shared-proton asymmetric stretching frequency within H2O x HF complexes. The extreme sensitivity of the proton transfer potential energy hypersurface to local hydrogen bonding topologies modulates its vibrational frequency from 2800 down to approximately 1300 cm(-1), the latter value being characteristic of solvation geometries that yield similar condensed-phase proton affinities for H2O and fluoride. By linking the local degree of ionization to the solvation pattern, we are able to propose a mechanism of ionization for HF in aqueous solutions and to explain some of their unusual properties at large concentrations. However, an important conclusion of broad scientific interest is our prediction that spectral signatures that are normally attributed to protonated water networks could also reveal the presence of strong hydrogen bonds between un-ionized acids and water molecules, with important consequences to spectroscopic investigations of biologically relevant proton channels and pumps.     

Advantages of simplicial partitioning for Lipschitz optimization problems with linear constraints

The well known DIRECT (DIviding RECTangles) algorithm for global optimization requires bound constraints on variables and does not naturally address additional linear or nonlinear constraints. A feasible region defined by linear constraints may be covered by simplices, therefore simplicial partitioning may tackle linear constraints in a very subtle way. In this paper we demonstrate this advantage of simplicial partitioning by applying a recently proposed deterministic simplicial partitions based DISIMPL algorithm for optimization problems defined by general linear constraints (Lc-DISIMPL). An extensive experimental investigation reveals advantages of this approach to such problems comparing with different constraint-handling methods, proposed for use with DIRECT. Furthermore the Lc-DISIMPL algorithm gives very competitive results compared to a derivative-free particle swarm algorithm (PSwarm) which was previously shown to give very promising results. Moreover, DISIMPL guarantees the convergence to the global solution, whereas the PSwarm algorithm sometimes fails to converge to the global minimum.     

Bifurcation of Nonlinear Bloch Waves from the Spectrum in the Gross–Pitaevskii Equation

We rigorously analyze the bifurcation of stationary so-called nonlinear Bloch waves (NLBs) from the spectrum in the Gross–Pitaevskii (GP) equation with a periodic potential, in arbitrary space dimensions. These are solutions which can be expressed as finite sums of quasiperiodic functions and which in a formal asymptotic expansion are obtained from solutions of the so-called algebraic coupled mode equations. Here we justify this expansion by proving the existence of NLBs and estimating the error of the formal asymptotics. The analysis is illustrated by numerical bifurcation diagrams, mostly in 2D. In addition, we illustrate some relations of NLBs to other classes of solutions of the GP equation, in particular to so-called out-of-gap solitons and truncated NLBs, and present some numerical experiments concerning the stability of these solutions.     

Spectral synthesis for coadjoint orbits of nilpotent Lie groups

We determine the space of primary ideals in the group algebra \(L^{1}(G) \) of a connected nilpotent Lie group by identifying for every \(\pi \in \widehat{G} \) the family \(\mathcal I^\pi \) of primary ideals with hull \(\{\pi \} \) with the family of invariant subspaces of a certain finite dimensional sub-space \(\mathcal P_Q^\pi \) of the space of polynomials \(\mathcal P(G) \) on G.