A ruthenium(II)-trithiacyclononane curcuminate complex: Synthesis,characterization, DNA-interaction,and cytotoxic activity

The coordination of ruthenium(II) complexes to anionic oxygen-based donors are very rare. This study describes a simple, one-pot method for obtaining [ruthenium(II)(trithiacyclononane)(curcumin)(S-DMSO)]Cl (1) in 37% yield. The structural characterization of complex 1 by elemental analysis, FT-IR, 1-D and 2-D NMR, ESI⁺-MS as well as UV–vis and fluorescence spectroscopies are presented. The DNA-melting temperature (T_m) assay shows that salmon sperm DNA (smDNA) in the presence of complex 1 has a higher melting temperature, with ΔT_m = 7.4 °C, while in the presence of curcumin the melting temperature remains unaltered. The in vitro cytotoxic activities of curcumin and complex 1 were investigated using the tumor human prostate cell line, PC-3, and the healthy cell line, PNT-2. Complex 1 is innocuous toward normal prostate epithelial cells and, whereas curcumin is toxic, with inhibition rates of ca. 35 and 65% at 50 and 80 μM, respectively. On the tumor cell line PC-3, complex 1 did not cause viability changes, whereas curcumin exhibited dose-dependent inhibition, with ca. 73% inhibition at the highest concentration tested, i.e. 80 μM. This study suggests that coordination with the trithiacyclononane ruthenium(II) scaffold stabilizes the photochemical properties of curcumin and strongly changes its biologic activity.     

Improvement of UV stability and mechanical properties of biopolyesters through the addition of β-carotene

β-carotene, the most abundant carotenoid in nature and a natural antioxidant, has been added at a concentration of 2 × 10⁻⁴ g per mL of polymer film forming solution to three biopolyester matrices, poly(lactic acid) (PLA), polycaprolactone (PCL) and polyhydroxybutyrate-co-valerate (PHBV). The dispersion and stability of the antioxidant within the films was studied using confocal Raman imaging spectroscopy, colorimetry and UV/visible spectrophotometry. The films were characterized in terms of thermal and mechanical properties in comparison with control films without β-carotene. Addition of β-carotene to the three biopolyesters studied resulted in significant increases in the deformation at break and lower Young modulus. This antioxidant is thought to act as a plasticizer in the biopolyesters, thus increasing their free volume and causing a change in their thermal properties. Moreover, when exposed to UV light the mechanical properties of the films with β-carotene were less affected displaying, in general, higher modulus and similar ultimate tensile strength while keeping the films more ductile than the pure films. Therefore, β-carotene can be potentially used as a natural additive to increase the UV stability of the biopolyesters.     

Application of thiophilic chromatography to deplete serum immunoglobulins in sample preparation for bidimensional electrophoresis

Serum is a typical sample for non-invasive studies in clinical research. Its proteome characterization is challenging, since requires extensive protein depletion. Methods used nowadays for removal of high-abundance proteins are expensive or show quite often a low loading capacity, which has strong repercussions on the number of samples and replicates per analysis.In order to deplete immunoglobulins (Igs) and albumin (HSA) from 1 mL serum samples, we have developed a protocol based on a combination of thiophilic chromatography, not previously used in clinical proteomics, and a HSA-specific resin. Ig/HSA-depleted samples, immunoglobulinome and albuminone were analyzed by 2-DE. Thiophilic chromatography, coupled with HSA-depletion, allows a good 2-DE resolution as well as the visualization of new spots. Moreover, it yields enough protein to evaluate technical variability and facilitate subsequent protein identification. To validate the protocol, we carried out a preliminary comparative study between triplicate Igs/HSA-depleted serum samples from healthy control individuals and recently diagnosed/untreated rheumatoid arthritis (RA) patients. RA patients showed several acute phase proteins, as well as additional serum proteins, differentially and significantly regulated.Therefore, thiophilic chromatography can be used as an efficient and economical method in 2-DE to deplete immunoglobulins from large human serum samples before a more extensive fractioning.     

The Asymptotic and Numerical Inversion of the Marcum Q‐Function

The generalized Marcum functions appear in problems of technical and scientific areas such as, for example, radar detection and communications. In mathematical statistics and probability theory these functions are called the noncentral gamma or the noncentral chi‐squared cumulative distribution functions. In this paper, we describe a new asymptotic method for inverting the generalized Marcum Q‐function and for the complementary Marcum P‐function. Also, we show how monotonicity and convexity properties of these functions can be used to find initial values for reliable Newton or secant methods to invert the function. We present details of numerical computations that show the reliability of the asymptotic approximations.     

New asymptotic representations of the noncentral t-distribution

New asymptotic approximations of the noncentral t distribution are given a generalization of the Student's t distribution. Using new integral representations, we give new asymptotic expansions not only for large values of the noncentrality parameter but also for large values of the degrees of freedom parameter. In some cases, we accept more than one large parameter. These results are not only in terms of elementary functions, but also in terms of the complementary error function and the incomplete gamma function. A number of numerical tests demonstrate the performance of the asymptotic approximations.     

DNA-templated assembly of dyes and extended π-conjugated systems

This feature article reports on the use of DNA as a template to assemble dyes and π-conjugated systems with the aim to construct functional multicomponent nanostructures that have a well-defined size, shape and sequence.     

Influence of the alkyl and alkoxy side chains on the electronic structure and charge-transport properties of polythiophene derivatives

Density Functional Theory has been used to study the structural, electronic and charge-transport properties of two regio-regular head-to-tail polythiophene derivatives, i.e. poly(3-hexyl-thiophene), P3HT, and poly(3-oxyhexyl-thiophene), P3OHT. The effect of substituents on the electronic structure was analyzed by means of bandwidth, bandgap, effective mass, total and partial densities of states and crystal orbital overlap populations. Electronic couplings were estimated from band diagrams as the splitting of the valence band. The neutral and cationic states of isolated oligomers were optimized using the supercell approximation. The hole-transfer rates and mobilities were evaluated according to Marcus's theory. Results provide a compelling illustration of the effect of side chains on the crystal packing, electronic structure and charge-transport properties. Thus, the hole mobility calculated for the alkyl derivative was 0.15 cm(2) V(-1) s(-1) (experimental mobility is 0.10 cm(2) V(-1) s(-1)), while the alkoxy derivative has a theoretical mobility of 0.49 cm(2) V(-1) s(-1). The obtained results hopefully could motivate experimentalists to try out P3OHT for an improved charge carrier mobility.     

On the zeros of the Scorer functions

Asymptotic approximations are developed for zeros of the solutions Gi(z) and Hi(z) of the inhomogeneous Airy differential equation . The solutions are also called Scorer functions. Tables are given with numerical values of the zeros.     

Synthesis and characterization of complexes of PdII with 2-aminopyridine

Summary The synthesis and identification of the compoundstrans-bis(2-aminopyridine)dichloropalladium(II) and tetrakis(2-aminopyridine)palladium(II) chloride are described. The infrared spectra are discussed, particularly the metal-halogen and metal-ligand vibrations. Thermal decomposition was studied by differential thermal analysis (DTA) and thermogravimetry (TG).     

Shedding Light on the Origin of Solid-State Luminescence Enhancement in Butterfly Molecules

Different molecular strategies have been carefully evaluated to produce solid-state luminescence enhancement (SLE) in compounds that show dark states in solution. A set of α-phenylstyrylarene derivatives with a butterfly shape have been designed and synthesised, for the first time, with the aim of improving the solid-state fluorescence emission of their parent styrylarene compounds. Although these butterfly molecules are not fluorescent in solution, one of them (1,2,4,5-tetra(α-phenylstyryl)benzene) exhibits a fluorescence quantum yield as high as 68 % in a drop-cast sample and 31 % in its crystalline form. In contrast, 1,3,5-tris(α-phenylstyryl)benzene and 4,6-bis(α-phenylstyryl)pyrimidine do not show SLE. A range of fluorescence spectroscopy experiments and DFT calculations were carried out to unravel the origin of different photophysical behaviour of these compounds in the solid state. The results indicate that a rational strategy to control the SLE effect in luminogens depends on a delicate balance between molecular properties and inter-/intramolecular interactions in the solid state.