Explanation of Anomalous Gas-Chromatographic (Gc) Behaviour in a Homologous Series of 2-Chloroethyl Phosphonic Acid Dialkyl Esters

Abstract

The study of GC separation of 2-chloroethylphosphonic acid di-n-alkyl (1–5 C atoms) esters (synthesised by us) on silicone stationary phases (OV-1, OV-17, OV-225) revealed a deviation from the expected linear dependence of retention indexes (RI) versus the number of C atoms of the alkyl chain: the first member of the series presents stronger retention than one can expect. This anomalous behaviour was observed especially on polar stationary phase (OV-225, see Figure l), and was emphasised with the increase of the column temperature. In an attempt to rationalise the above mentioned facts, we tried to relate the RI values to a global polarity parameter: the dipole moment, μ. The μ values for ClC₂H₄P(O)(OR)₂ were calculated by a method described in [1] (tested by comparing the calculated μ values with experimental ones for alkyl phosphonic acid dialkylesters), using molecular mechanics (COSMIC package) in the search of the conformational space, AM1 method (MOPAC 6.0) for the μ values of the conformers, and Boltzmann distribution for the global value (see Table I). At low temperature, the μ values are not related to the Kovats indexes. Those calculated at 200°C (column temperature range) demonstrate that, indeed, only in the case of the methyl derivative, the temperature rising led to a higher μ (enhanced population of the more polar conformers: ac position for the C-Ethyl group - ac for the Cl, μ ≈ 27 D, or ±ap for one R, μ ≈ 3.8 ÷ 4.3 D). It can be concluded that dipole-dipole forces contribute to the separation process of the first members of the series.     

Synthesis of Mixed Alkylphosphites and Alkylphosphates

Some mixed phosphites having two different alkyl chain were obtained as forerunners for mixed phosphates Mixed dialkyl phosphates were obtained in good yields (40-80%) by phase transfer catalysis in liquid-liquid sistem, starting from different dialkyl phosphites and aliphatic alcohols. The reaction conditions were optimized in order to obtain good yields in phosphites and phosphates respectively. Compounds were analyzed by IR, P 31 -NMR.     

Isotopic analyses by ICP-MS in clinical samples

This critical review focuses on inductively coupled plasma mass spectrometry (ICP-MS) based applications for isotope abundance ratio measurements in various clinical samples relevant to monitoring occupational or environmental exposure, human provenancing and reconstruction of migration pathways as well as metabolic research. It starts with a brief overview of recent advances in ICP-MS instrumentation, followed by selected examples that cover the fields of accurate analyte quantification using isotope dilution, tracer studies in nutrition and toxicology, and areas relying upon natural or man-made variations in isotope abundance ratios (Pb, Sr, actinides and stable heavy elements). Finally, some suggestions on future developments in the field are provided.     

Combined Experimental and Theoretical Insights into the Corrosion Inhibition Activity on Carbon Steel Iron of Phosphonic Acids

The inhibition effect of N,N′-phosphonomethylglycine (PMG) and vinyl phosphonic acid (VPA) on the 3% NaCl acidic solution corrosion of carbon steel iron was studied at different immersion times by potentiodynamic polarization, electrochemical impedance spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and computational methods. It is found from the polarization studies that PMG and VPA behave as mixed-type inhibitors in NaCl. Values of charge transfer resistance (R_ct) and double layer capacitance (C_dl) in the absence and presence of inhibitors are determined. The PMG and VPA inhibitors were capable of inhibiting the corrosion process up to ≈91% and ≈85%, respectively. In the presence of PMG, the synergic effect of chlorine ions was observed. Density functional theory (DFT) was engaged to establish the adsorption site of PMG, VPA, and their deprotonated states. For studied compounds, the resulted values of E_LUMO, E_HOMO, energy gap (∆E), dipole moment (μ), electronic hardness (η), global softness (σ), electrophilic index (ω), and the electronic potential map are in concordance with the experimental data results regarding their corrosion inhibition behavior and adsorption on the metal surface.     

Bulk and surface electron transport in topological insulator candidate YbB6–δ

We report the study of transport and magnetic properties of the YbB_6–δsingle crystals grown by inductive zone melting. A strong disparity in the low temperature resistivity, Seebeck and Hall coefficients is established for the samples with the different level of boron deficiency. The effective parameters of the charge transport in YbB_6–δ are shown to depend on the concentration of intrinsic defects, which is estimated to range from 0.09% to 0.6%. The pronounced variation of Hall mobility μ_H found for bulk holes is induced by the decrease of transport relaxation time from τ ≈ 7.7 fs for YbB_5.994 to τ ≈ 2.2 fs for YbB_5.96. An extra contribution to conductivity from electrons with μ_H≈ –1000 cm² V^–1 s^–1 and the very low concentration n /n_Yb≈ 10^–6 discovered below 20 K for all the single crystals under investigation is suggested to arise from the surface electron states appeared in the inversion layer due to the band bending. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

On the Stability of Pt-Based Catalysts in HBr/Br2 Solution

Stability studies on supported metal nanoparticles are essential for gaining insight into the design and optimization of high-performance materials. In this work, the dissolutions of Pt-based catalysts in HBr/Br₂ mixture of various concentration regimes were studied and correlated with material structural properties. The dissolution of metal nanoparticles was enhanced by adding Br₂ to the HBr solution. Comparing with commercial Pt/C catalyst, the well-alloyed PtIr/C catalyst was observed to exhibit high resistance towards dissolution. In addition, regulating the accessibility of the metal sites to dissolution-inducing species contributed to the marked stability of the nanoparticles in HBr/Br₂ solutions, as shown for the surface-modified PtIr/C catalysts with organic diamine molecules.     

Coercivity of Combined Boundary Integral Equations in High‐Frequency Scattering

We prove that the standard second‐kind integral equation formulation of the exterior Dirichlet problem for the Helmholtz equation is coercive (i.e., sign‐definite) for all smooth convex domains when the wavenumber k is sufficiently large. (This integral equation involves the so‐called combined potential, or combined field, operator.) This coercivity result yields k‐explicit error estimates when the integral equation is solved using the Galerkin method, regardless of the particular approximation space used (and thus these error estimates apply to several hybrid numerical‐asymptotic methods developed recently). Coercivity also gives k‐explicit bounds on the number of GMRES iterations needed to achieve a prescribed accuracy when the integral equation is solved using the Galerkin method with standard piecewise‐polynomial subspaces. The coercivity result is obtained by using identities for the Helmholtz equation originally introduced by Morawetz in her work on the local energy decay of solutions to the wave equation. © 2015 Wiley Periodicals, Inc.     

Chaetopterus variopedatus Bioluminescence: A Review of Light Emission within a Species Complex

Chaetopterus variopedatus has been studied for over a century in terms of its physiology, ecology and life history. One focus of research is on its intrinsic bioluminescent emissions, which can be observed as a blue light emitted from the extremities of individual body segments, or as a secreted mucus. Even though research shows that C. variopedatus is a species complex miscategorized as a single species, all of the variants of this polychaete produce light, which has been investigated in terms of both physiology and biochemistry. Despite decades of study, there are still many questions about the luminescence reaction, and, as of yet, no clear function for light emission exists. This review summarizes the current knowledge on C. variopedatus luminescence in addition to briefly describing its morphology, life cycle and ecology. Possible functions for luminescence were discussed using observations of specimens found in Brazil, along with a comparison of previous studies of other luminescent organisms. Further study will provide a better understanding of how and why C. variopedatus produces luminescence, and purifying the protein and luciferin involved could lead to new bioanalytical applications, as this reaction is unique among all known luminescent systems.     

Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

Compounds based on new cyanide cluster anions [{Mo₆I₈}(CN)₆]^2–, trans-[{Mo₆I₈}(CN)₄(MeO)₂]^2– and trans-[{W₆I₈}(CN)₂(MeO)₄]²⁻ were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo₆I₈}⁴⁺ and {W₆I₈}⁴⁺ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo₆I₈} and {W₆I₈} cluster cores can be achieved by coordination of cyanide ligands.