Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells

The chiral cationic complex [Ru(η¹-OAc)(CO)((R,R)-Skewphos)(phen)]OAc ( 2 ^R ), isolated from reaction of [Ru(η¹-OAc)(η²-OAc)(R,R)-Skewphos)(CO)] ( 1 ^R ) with phen, reacts with NaOPiv and KSAc affording [RuX(CO)((R,R)-Skewphos)(phen)]Y (X=Y=OPiv 3 ^R ; X=SAc, Y=OAc 4 ^R ). The corresponding enantiomers 2 ^S - 4 ^S have been obtained from 1 ^S containing (S,S)-Skewphos. Reaction of 2 ^R and 2 ^S with (S)-cysteine and NaPF₆ at pH=9 gives the diastereoisomers [Ru((S)-Cys)(CO)(PP)(phen)]PF₆ (PP=(R,R)-Skewphos 2 ^R -Cys; (S,S)-Skewphos 2 ^S -Cys). The DFT energetic profile for 2 ^R with (S)-cysteine in H₂O indicates that aquo and hydroxo species are involved in formation of 2 ^R -Cys. The stability of the ruthenium complexes in 0.9 % w/v NaCl solution, PBS and complete DMEM medium, as well as their n-octanol/water partition coefficient (logP), have been evaluated. The chiral complexes show high cytotoxic activity against SW1736, 8505 C, HCT-116 and A549 cell lines with EC₅₀ values of 2.8–0.04 μM. The (R,R)-Skewphos derivatives show higher cytotoxicity compared to their enantiomers, 4 ^R (EC₅₀=0.04 μM) being 14 times more cytotoxic than 4 ^S against the anaplastic thyroid cancer 8505 C cell line.     

Diffusion determines the recurrent graph

We consider diffusion on discrete measure spaces as encoded by Markovian semigroups arising from weighted graphs. We study whether the graph is uniquely determined if the diffusion is given up to order isomorphism. If the graph is recurrent then the complete graph structure and the measure space are determined (up to an overall scaling). As shown by counterexamples this result is optimal. Without the recurrence assumption, the graph still turns out to be determined in the case of normalized diffusion on graphs with standard weights and in the case of arbitrary graphs over spaces in which each point has the same mass.     

Solvent effect on the thermodynamics of Ag(I) coordination to tripodal polypyridine ligands

An investigation on the thermodynamics of complex formation between Ag(I) ion and two tripodal ligands tris[(2-pyridyl)methyl]amine (TPA) and 6,6′-bis-[bis-(2-pyridylmethyl)aminomethyl]-2,2′-bipyridine (BTPA) has been carried out in the aprotic solvents dimethylsulfoxide (DMSO) and dimethylformamide (DMF) by means of potentiometry and titration calorimetry. The results for TPA are compared with those already obtained for other aliphatic tripodal polyamines. In general, the TPA ligand forms complexes less stable than 2,2′,2″-triaminotriethylamine (TREN) and tris(2-(methylamino)ethyl)amine (Me₃TREN) as a result of the combination of higher structural rigidity of TPA and lower σ-donor ability of pyridinic moieties with respect to primary and secondary amines. The same trend is found if the stability of Ag(I) complex with TPA is compared with that of tris(2-(dimethylamino)ethyl)amine (ME₆TREN), despite the pyridinic nitrogen is formally a tertiary one. Theoretical calculations run to explain the reasons of this weaker interaction indicate that this difference is due to solvation, rather than to steric or σ-donor effects. The ligand BTPA is able to form bimetallic species whose relative stability is largely influenced by the different solvation of Ag(I) ion in DMSO and DMF rather than by the difference in the dielectric constants of these two media.     

Simultaneous micellar electrokinetic chromatographic determination of isomeric fatty acid hydroperoxides and corresponding hydroxy fatty acids

The high selectivity and efficiency of micellar electrokinetic chromatography with a borax-sodium dodecylsulfate (SDS) or meglumin-SDS buffer make possible the rapid separation of hydroperoxy and hydroxy fatty acids and the non-oxidised unsaturated fatty acids from which they are derived. Nearly all the isomers of the hydroperoxides and hydroxy fatty acids derived from oleic, linoleic, alpha- and gamma-linolenic and arachidonic acids can be determined both qualitatively and quantitatively within ca. 10 min. The system has as many as 1 x 10(6) theoretical plates, and the detection limits with UV diode array detection at 195 or 234 nm are in the micromolar range.     

Ultrafast all-optical demultiplexer based on monolithic Mach–Zehnder interferometer with integrated semiconductor optical amplifiers

A monolithically integrated and fully packaged Mach–Zehnder interferometer with semiconductor optical amplifiers (MZI-SOA) is demonstrated as polarisation-independent high-speed demultiplexer for up to 160 Gbit/s optical time division multiplexed (OTDM) data streams.     

Decentralized CRONE control of nonsquare multivariable systems in path-tracking design

In this paper, motion control and robust path tracking were extended to nonsquare MIMO (Multi-Input Multi-Output) systems having more outputs than inputs. A path-tracking design based on fractional prefilter approach has been developed and extended to control nonsquare MIMO systems. The nonsquare relative gain array (NRG) is used to assess the performance of nonsquare control systems based on steady-state information. The CRONE control approach developed for multivariable plants based on third-generation SISO CRONE methodology is combined with MIMO-QFT (Quantitative Feedback Theory) robust design methodology, taking into account the plant uncertainties. After the determination of CRONE controller, the parameter of prefilter has been optimized considering physical constraints of actuators and the tracking performance specifications. The proposed design is applied to an example.     

Improvements to the compressed-sample (CS) technique for MALDI-TOF mass spectrometry

A recently developed solvent-free compressed-sample technique for matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) analysis allows the reproducible analysis of synthetic polymers and peptides up to 3,500 Da. In this work, we present an improvement in resolution, an increase in intensity and a decrease of the variation coefficient, as illustrated by the analysis of PEG 2000 and MALDI imaging experiments. These advantages were achieved by homogenization of the electrical field, which was disturbed by the drills in the original MALDI target. In order to homogenize the electrical field, a new target with smaller drills was developed, metal powder was added to the matrix/analyte mixture and a round laser raster was used. Furthermore, a ball mill was implemented for the sample preparation to replace the extremely user-dependent grinding in a mortar. The new conditions were successfully applied to the quantification of several peptides of higher molecular weight and gave higher precision than had previously been achieved with the compressed-sample technique.