Thermodynamic study of (heptane + amine) mixtures. III: Excess and partial molar volumes in mixtures with secondary,tertiary, and cyclic amines at 298.15 K

Excess molar volumes V^E at 298.15 K were determined by means of a vibrating tube densimeter for binary mixtures of {heptane + open chain secondary (diethyl to dibutyl) and tertiary (triethyl to tripentyl) amines} as well as for cyclic imines (C₂, C₃, C₄, C₆, and C₇) and primary cycloalkylamines (C₅, C₆, C₇, and C₁₂). The V^E values were found positive for mixtures involving small size amines, with V^E decreasing as the size increases. Negative V^E’s were found for tributyl- and tripentylamine, heptamethylenimine, and cyclododecylamine. Mixtures of heptane with cycloheptylamine showed an s-shaped curve.Partial molar volumes $V^{°}$ of amines at infinite dilution in heptane were obtained from V^E and compared with $V^{°}$ of hydrocarbons and other classes of organic compounds taken from literature. An additivity scheme, based on the intrinsic volume approach, was applied to estimate group (CH₃, CH₂, CH, C, NH₂, NH, N, OH, O, CO, and COO) contributions to $V^{°}$. These contributions, the effect of cyclization on $V^{°}$, and the limiting slope of the apparent excess molar volumes were discussed in terms of solute–solvent and solute–solute interactions.     

Promising anticancer mono- and dinuclear ruthenium(III) dithiocarbamato complexes: systematic solution studies

During the last decade, our research group has prepared a number of metal dithiocarbamato derivatives of Pt, Pd and Au that were expected to resemble the main features of cisplatin together with higher activity, improved selectivity and bioavailability, and lower side-effects. Furthermore, we have already published the synthesis, characterization and in vitro cytotoxicity studies of novel ruthenium(III) dithiocarbamato complexes such as [RuL(3)] monomers (11) and α-[Ru(2)L(5)]Cl dimers (12) with five different dithiocarbamate ligands. As both the monomer and the dinuclear complexes have shown significant antitumor activity in different human tumor cell lines, we decided to widen the characterization studies and to analyse thoroughly their behavior in physiological-like medium by UV-visible and CD spectroscopy. In the present paper we report on the crystal structure of [Ru(DMDT)(3)], [Ru(PDT)(3)] and [Ru(ESDT)(3)] complexes and we determine the spin state of the paramagnetic Ru(III) by means of Evans' method. Then, we discuss in detail the UV-visible spectral data of the complexes in different medium. All the studied complexes are stable in dimethyl sulfoxide, and show low solubility in phosphate buffered saline solution, particularly the monomer species, even at low concentration, while increased solubility for both types of complexes have been found in the presence of bovine serum albumin (BSA). Moreover, no changes on the coordination sphere of the metal, as well as no direct interaction between the BSA protein and the complex have been identified by UV-visible spectroscopy. However, some conformational changes on the BSA structure, induced by the ruthenium(III) complexes have been confirmed by CD spectroscopy, indicating a probable secondary electrostatic interaction between the metal complex and the peptide. In addition, no significant interaction has been demonstrated with the components of Dulbecco's Modified Eagle's Medium, used for the in vitro assays.     

On the antibacterial activity of roots of Capparis spinosa L

A decoction of Capparis spinosa L. roots, widely used in the traditional folk medicine of southern Italy, was prepared and submitted to antibacterial activity tests, which showed an interesting bacteriostatic activity on the growth of Deinococcus radiophilus. Heterocyclic compounds were also recovered from the chloroformic extract of the roots.     

Using multiple short-end injections to develop fast electrophoretic separations--applications in iodide analysis

The aim of this study was to develop a fast CE separation method by using multiple short-end injections in a capillary coated with quaternary ammonium chitosan (HACC), in order to determine the iodide content of pharmaceutical formulations. The BGE was composed of 20 mM tris(hydroxymethyl)aminomethane and 11 mM hydrochloric acid, at pH 8. The internal standard used was thiocyanate. Separations were performed in a fused silica capillary (32 cm total length, 8.5 cm effective length and 50 μm i.d.) coated with HACC and direct UV detection at 220 nm. EOF was modified by flushing the capillary with polymeric solution, resulting in a semi-permanent coating of controlled and stable EOF. The EOF was anodic at pH 8. Different strategies, using single and multiple injection short-end configurations, were studied to develop a CE method that resulted in a maximum number of iodide samples analyzed per hour: one plug and flush (Sflush) 35 samples/h, one plug without flush (SWflush) 76 samples/h, four plugs and flush (Mflush) 61 samples/h, and four plugs without flush (MWflush) 80 samples/h. Using the multiple injection configuration, it was possible to inject up to four plugs using spacer electrolytes with good separation efficiency and selectivity. The voltage application time needed to separate the eight peaks (iodide and thiocyanate) with MWflush was only 12s. The method was validated and samples were analyzed using MWflush. Good linearity (R(2)>0.999); a limit of detection 0.4 mg L(-1); intermediate precision better than 3.8% (peak area) and recovery in the range of 99-102% were obtained.     

Strategic simulation models as a new methodological approach: an application to information technologies integration,lean/just-in-time and lead-time

Central European Journal of Operations Research - Hypothesis contrast using statistical models with Structural Equations is a technique widely used in Supply Chain Management research. However,...     

Structural and thermodynamic studies of the interaction of distamycin A with the parallel quadruplex structure [d(TGGGGT)]4

The complex between distamycin A and the parallel DNA quadruplex [d(TGGGGT)]4 has been studied by 1H NMR spectroscopy and isothermal titration calorimetry (ITC). To unambiguously assert that distamycin A interacts with the grooves of the quadruplex [d(TGGGGT)]4, we have analyzed the NMR titration profile of a modified quadruplex, namely [d(TGGMeGGT)]4, and we have applied the recently developed differential frequency-saturation transfer difference (DF-STD) method, for assessing the ligand-DNA binding mode. The three-dimensional structure of the 4:1 distamycin A/[d(TGGGGT)]4 complex has been determined by an in-depth NMR study followed by dynamics and mechanics calculations. All results unequivocally indicate that distamycin molecules interact with [d(TGGGGT)]4 in a 4:1 binding mode, with two antiparallel distamycin dimers that bind simultaneously two opposite grooves of the quadruplex. The affinity between distamycin A and [d(TGGGGT)]4 enhances ( approximately 10-fold) when the ratio of distamycin A to the quadruplex is increased. In this paper we report the first three-dimensional structure of a groove-binder molecule complexed to a DNA quadruplex structure.     

The Cohomology of the Universal Steenrod Algebra

The mod 2 universal Steenrod algebra Q is a homogeneous quadratic algebra closely related to the ordinary mod 2 Steenrod algebra and the Lambda algebra introduced in [1]. In this paper we show that Q is Koszul. It follows by [7] that its cohomology, being purely diagonal, is isomorphic to a completion of Q itself with respect to a suitable chain of two-sided ideals.