On the comparative study of three silver coins of the IIIrd century B.C. minted in Korkyra, Dyrrachion and by the Illyrian king Monounios

The microstructure of three silver coins dating back to the IIIrdcentury B.C. from the Illyrian King Monounios, the ancient Greek city of Dyrrachion and the ancient Greek city of Korkyra was studied with XRF, PIXE, microhardness measurements, and light and electron microscopy. From this investigation it turned out that these coins have different chemical compositions and different microstructures. The as-collected data allow the determination of a possible minting method. The Korkyra coin was probably hot-worked or cold-worked and annealed, while after cooling, it was cold-worked again. The coin of King Monounios is composed by equi-axed grains which are overrun by slip lines. Consequently it is likely that this coin was casted and then cold-struck. Finally the coin from Dyrrachion is characterized by small-sized grains and strain lines and as a result this coin was probably cold-struck. PACS 07.60.Pb; 78.70.En; 68.37.Ef; Hk; Lp; Nq; 61.66.Bi; 61.72.Mm     

Synthesis, spectral and electrochemical study of coordination molecules Cu4OX6L4: 3-cyanopyridine Cu4OBrnCl(6?n)(3-CNpy)4 complexes

New 4-cyanopyridine halide and mixed-halide Cu₄OBr _n Cl_(6−n)(4-CNpy)₄ complexes (4-CNpy = 4-cyanopyridine, n = 0–6) were synthesised, characterised, and studied by infrared spectra, electronic spectra, and cyclic voltammetry. Infrared spectra revealed donor-acceptor vibrational couplings of the Cu₄O, Cu-Cl, and Cu-N stretching vibrations with the in-plane and out-of-plane pyridine ring vibrations. The infrared spectra, electronic spectra, and half-wave potentials correspond to a weak donor and a strong acceptor behaviour of the 4-cyanopyridine ligands and to π-back bonding, Cu(II)→pyridine rings. The results were compared with the related pyridine and 4-substituted pyridine complexes.     

Pressurized liquid extraction as a novel sample pre-treatment for trace element leaching from biological material

Pressurized liquid extraction (PLE), commonly used for organic compounds extraction, has been applied for trace element leaching from marine biological material in order to determine major and trace elements (Al, As, Cd, Co, Cu, Fe, Hg, Li, Mn, Pb, Se, Sr, V and Zn). The released elements by formic acid PLE have been evaluated by inductively coupled plasma-optical emission spectrometry (ICP-OES). Different variables, such as formic acid concentration, extraction temperature, static time, extraction steps, pressure, mean particle size and diatomaceous earth (DE) mass/sample mass ratio were simultaneously studied by applying an experimental design approach (Plackett-Burman design (PBD) and central composite design (CCD)). Results showed that the extraction temperature was statistically significant (confidence interval of 95%) for most of the elements (high metal releasing was achieved at high temperatures). In addition, formic acid concentration was also statistically significant (confidence interval of 95%) for metals such as Cd and Cu. Most of the metals can be extracted using the same PLE operating conditions (formic acid concentration of 1.0 M, extraction temperature at 125 °C, static time of 5 min, one extraction step, extraction pressure at 500 psi and DE mass/sample mass ratio of 2). Taking in mind PLE requirements at the optimised operating conditions (125 °C), a time of 6 min is needed to pre-heat the cell. Therefore, the PLE assisted multi-element leaching is completed after 12 min. Analytical performances, such as limits of detection and quantification, repeatability of the over-all procedure and accuracy, by analysing GBW-08571, DORM-2, DOLT-3 and TORT-2 certified reference materials, were finally assessed.     

Falloff curves for the recombination reaction Cl + FC(O)O + M --> FC(O)OCl + M

The pressure dependence of the recombination reaction Cl + FC(O)O + M --> FC(O)OCl + M has been investigated at 296 K. FC(O)O radicals and Cl atoms were generated by laser flash photodissociation of FC(O)OO(O)CF at 193 nm in mixtures with Cl2 and He or SF6 over the total pressure range 8-645 Torr. The measured FC(O)O radical and F atom yields in the photolysis are 0.33 +/- 0.06 and 0.67 +/- 0.06. The reaction lies in the falloff range approaching the high-pressure limit. The extrapolations toward the limiting low- and high-pressure ranges were carried out using a reduced falloff curves formalism, which includes a recent implementation for the strong-collision broadening factors. The resulting values for the low-pressure rate coefficients are (2.2 +/- 0.4) x 10(-28)[He], (4.9 +/- 0.9) x 10(-28)[SF6], (1.9 +/- 0.3) x 10(-28)[Cl2] and (5.9 +/- 1.1) x 10(-28)[FC(O)OO(O)CF] cm3 molecule(-1) s(-1). The derived high-pressure rate coefficient is (4.4 +/- 0.8) x 10(-11) cm3 molecule(-1) s(-1). For the reaction Cl + FC(O)OCl --> Cl2 + FC(O)O a rate coefficient of (1.6 +/- 0.3) x 10(-11) cm3 molecule(-1) s(-1) was determined. The high-pressure rate coefficient was theoretically interpreted using SACM/CT calculations on an ab initio electronic potential computed at the G3S level of theory. Standard heat of formation values of -99.9 and -102.5 kcal mol(-1) were computed at the G3//B3LYP/6-311++G(3df,3pd) level of theory for cis-FC(O)OCl and trans-FC(O)OCl, respectively. The computed electronic barrier for the conversion between the trans and cis conformers is 8.9 kcal mol(-1). On the basis of the present results, the above reactions are expected to have a negligible impact on stratospheric ozone levels.     

Stereoselective syntheses of heptaprenylphosphoryl β-d-arabino-and β-d-ribo-furanoses

The stereoselective syntheses of heptaprenylphosphoryl β-d-arabinofuranose and heptaprenylphosphoryl β-d-ribofuranose are described. In the synthesis of the d-arabino product, the stereoselectivity was achieved by the coupling of a suitably protected β-d-arabinofuranosyl phosphate intermediate with an activated form of heptaprenol and subsequent deprotection. In the case of the ribo-analog, the desired β-anomer could be obtained by the more convenient phosphoramidite method. The products were successfully employed in the mycobacterial epimerase assay.     

Indican determination in urine: Application for urine determination in adulterated cow milk

A spectrophotometric procedure for the determination of indican in urine based in Jolles' reaction, modified by Bermejo-Martínez and Barrera-Ramallo, is described; and it is applied for the determination of urine in adulterated cow milk, until addition of 2% human urine is estimated.     

On vertical skew symmetric almost contact 3-structures

We consider a (2m + 3)-dimensional Riemannian manifold M(ξ _r, η^r, g ) endowed with a vertical skew symmetric almost contact 3-structure. Such manifold is foliated by 3-dimensional submanifolds of constant curvature tangent to the vertical distribution and the square of the length of the vertical structure vector field is an isoparametric function. If, in addition, M(ξ _r, η^r, g ) is endowed with an f -structure φ, M, turns out to be a framed f−CR-manifold. The fundamental 2-form Ω associated with φ is a presymplectic form. Locally, M is the Riemannian product of two totally geodesic submanifolds, where is a 2m-dimensional Kaehlerian submanifold and is a 3-dimensional submanifold of constant curvature. If M is not compact, a class of local Hamiltonians of Ω is obtained.     

Demonstration of a HeNe/CH4-based optical molecular clock

We implement a simple optical clock based on the F2(2) [P(7), v3] optical transition in methane. A single femtosecond laser's frequency comb undergoes difference frequency generation to provide an IR comb at 3.39 microm with a null carrier-envelope offset. This IR comb provides a phase-coherent link between the 88-THz optical reference and the rf repetition rate. Comparison of the repetition rate signal with a second femtosecond comb stabilized to molecular iodine shows an instability of 1.2 x 10(-13) at 1 s, limited by microwave detection of the repetition rates. The single-sideband phase noise of the microwave signal, normalized to a carrier frequency of 1 GHz, is below -93 dBc/Hz at 1-Hz offset.