Potential cytotoxic and amoebicide activity of first row transition metal compounds with 2,9-bis-(2',5'-diazahexanyl)-1,1-phenanthroline (L1)

A new synthetic pathway was reported to obtain N6 donor ligand 2,9-bis-(2',5'-diazahexanyl)-1,10-phenanthroline (L1) and its coordination compounds of essential divalent metal ions Mn, Fe, Co, Ni, Cu and Zn. Complete characterization of all compounds was done with the conventional techniques. Crystal structures of [NiL1](PF(6))(2) and [ZnL1](PF(6))(2)·H(2)O were also reported. Electrochemical studies have shown an active participation of the aromatic moiety of the ligand in redox reactions. The in vitro tests of the cytotoxic activity against human tumour cell lines HeLa (cervix) and CHP-212 (neuroblastoma) showed that all coordination compounds that involve redox active metal ions exhibit noteworthy antiproliferative activity, superior in all cases to cisplatin. [CuL1](2+) showed the lower IC(50) value in the HeLa cell line with 1.84 μM, meanwhile, [CoL1](2+) showed the lower value in neuroblastoma CHP-212 with IC(50) = 45.28 μM. None of these compounds were active against the SK-N-SH neuroblastoma cell line. In Entamoeba histolytica cultures, remarkable nanomolar IC(50) values were found for [NiL1](2+) and [MnL1](2+) with 60 nM and 80 nM respectively, improving the antiproliferative activity more than 1000 times compared with the first choice drug for clinical treatments of human amoebiasis, metronidazole. On the other hand, a free ligand does not show antiproliferative activity either on human tumor cell lines or on Entamoeba histolytica trophozoites, highlighting the role played by metal ions to produce cytotoxicity in tumor cells and protozoa systems.     

Non-conventional coordination of cavity-confined metal centres

WIDEPHOS, a β-cyclodextrin cavitand bearing two introverted P(III) donor atoms, readily accommodates two converging Au-X fragments (X = Cl, Br, I). In the corresponding [(WIDEPHOS)(AuX)(2)] complexes, severe steric crowding within the cavity results in one of the P-Au-X rods deviating from linearity, as revealed by an X-ray diffraction study and unusual (31)P magnetic shielding of one of the two phosphorus signals. The cavitand ligand is also suited for hosting strained dipalladium moieties with a single chlorido bridge, thereby forming dynamic complexes in which ligand coordination to one of the metal centres occurs via an oschelating P,O-subunit.     

Donor-π-Acceptors Containing the 10-(1,3-Dithiol-2-ylidene)anthracene Unit for Dye-Sensitized Solar Cells

Two donor-acceptor molecular tweezers incorporating the 10-(1,3-dithiol-2-ylidene)anthracene unit as donor group and two cyanoacrylic units as accepting/anchoring groups are reported as metal-free sensitizers for dye-sensitized solar cells. By changing the phenyl spacer with 3,4-ethylenedioxythiophene (EDOT) units, the absorption spectrum of the sensitizer is red-shifted with a corresponding increase in the molar absorptivity. Density functional calculations confirmed the intramolecular charge-transfer nature of the lowest-energy absorption bands. The new dyes are highly distorted from planarity and are bound to the TiO(2) surface through the two anchoring groups in a unidentate binding form. A power-conversion efficiency of 3.7?% was obtained with a volatile CH(3) CN-based electrolyte, under air mass 1.5 global sunlight. Photovoltage decay transients and ATR-FTIR measurements allowed us to understand the photovoltaic performance, as well as the surface binding, of these new sensitizers.     

Percolation of Trace Amounts of Linear Polymers in Melts of Cyclic Polymers

Melts of CPs, intentionally contaminated with small fractions of LPs, are studied using the bond fluctuation model to probe the extreme sensitivity of the rheology to trace amounts of linear chains. Using primitive path analysis to compute the number of entanglements on the molecules, the threshold concentration at which LPs percolate through the system is calculated using a mean‐field theory. It is found that the percolation threshold decreases with the molecular weight, and is approximately 25–30 times smaller than the overlap concentration of the linear chains for the longest polymers studied. These simulations help to understand and justify the approximations made in earlier theoretical investigations.

     

Different kinetics of photoinactivation of photosystem I-mediated electron transport and P700 in isolated thylakoid membranes

Photoinactivation kinetics of photosystem I (PSI)-mediated electron transport rate was compared to that of P700 content at room (22 degrees C) and low (4 degrees C) temperatures in isolated spinach thylakoid membranes. The high light treatment was carried out under aerobic and anaerobic conditions. At 22 degrees C the decrease of electron transport rate showed first order exponential kinetics. The amount of P700 decreased linearly, being less affected in the first hours of illumination. During photoinhibition at 4 degrees C in the presence of oxygen, the kinetics of inactivation of PSI photochemical activity and the content of P700 were different. It was found that 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) had different protective effect on the electron transport rate and on P700 content at both temperatures. Treatment with high light intensity under N(2) atmosphere had no effect on the electron transport rate or P700 content. The possible degradation of PSI reaction centre proteins was determined using immunoblot methods. In the presence of linear electron transport at 22 degrees C correlation between formation of toxic hydroxyl radicals and inhibition of oxygen uptake was observed.     

The energetics of the isomeric anthrols

We report the results of geometry optimized MP2(FULL)/6-31G(d) quantum chemical calculations with zero-point vibrational energies and thermal corrections of the isomeric 1-, 2- and 9-anthrols and the tautomeric anthrone. We find that 1- and 2-anthrols have nearly the same enthalpy of formation and are some 6?kJ?mol^?1 more stable than their 9-isomer in accord with intuition based on steric hindrance. We find that anthrone is more stable than 9-anthrol by 13.7 ± 6.4?kJ?mol^?1, in satisfactory agreement with the value of 23 ± 8?kJ?mol^?1 suggested elsewhere by experiment and its associated analysis.     

Hepatic sarcoidosis: MR appearances in patients with chronic liver disease

Purpose

To describe the MR appearances of hepatic sarcoidosis in patients with chronic liver disease and correlate the results with clinical stage of disease as measured with the Mayo end-stage liver disease (MELD) score.

Materials and methods

Twenty patients with chronic liver disease and histopathological diagnosis of hepatic sarcoidosis who underwent MR imaging were included in this study. Two abdominal radiologists retrospectively reviewed all images for the presence of cirrhosis, imaging pattern of the liver, intrahepatic biliary dilatation, presence of areas of parenchymal atrophy, presence of splenic nodules and lymphadenopathy. Imaging findings were correlated with the MELD score.

Results

Of the patients, 14/20 had imaging findings of cirrhosis, 9/20 had a large macronodular pattern of liver cirrhosis and 5/20 had a diffuse pattern of liver cirrhosis. Peripheral wedge-shaped areas of parenchymal atrophy were observed in 10 patients. The combination of a central macronodular pattern and peripheral atrophy was observed in 9/20 patients. The pattern of cirrhosis had statistically significant correlation with the presence of wedge-shaped areas of parenchymal atrophy (p < 0.005). No statistically significant difference was revealed between the clinical score of patients who had imaging findings consistent with cirrhosis and those who did not.

Conclusion

MR imaging appearances of chronic sarcoid liver disease are diverse and do not appear to correlate with severity of clinical disease. Large central regenerative nodules and wedge-shaped areas of peripheral parenchymal atrophy are frequent findings and may help to suggest the diagnosis.     

Mimetic trust and intra‐organizational network dynamics

Dynamic network models based on the homophily principle are criticized for neglecting organizational context conditions and the impact of role structures on the evolution of intra‐organizational trust networks. Using a neo‐institutional framework it is argued that individuals in competitive environments will attempt to reduce uncertainty about the trustworthiness of potential trustees by imitating the sociometric choice behavior of persons in similar network positions. Three hypotheses are developed. The positional trust hypothesis predicts that individuals tend to trust other actors who occupy a similar network position as themselves. The mimetic trust hypothesis argues that individuals trust actors who are trusted by persons in their own network position. Finally, the advisory trust hypothesis claims that individuals prefer to maintain trust relations to persons occupying a position of third party intermediary than to persons in other positions. An exploratory empirical test of the hypotheses is carried out by reanalyzing a longitudinal network study of the relationships among 25 salesmen in the furniture department of a North American retail sales store during the 1950s. Blockmodelling procedures are used to identify structural positions in the networks, and log‐linear analysis is applied to determine stability of choices within and between structural positions. The results support the mimetic trust and the advisory trust hypothesis.     

Ornstein–Uhlenbeck processes time changed with additive subordinators and their applications in commodity derivative models

We characterize Ornstein–Uhlenbeck processes time changed with additive subordinators as time-inhomogeneous Markov semimartingales, based on which a new class of commodity derivative models is developed. Our models are tractable for pricing European, Bermudan and American futures options. Calibration examples show that they can be better alternatives than those developed in Li and Linetsky (2012)  [6]. Our method can be applied to many other processes popular in various areas besides finance to develop time-inhomogeneous Markov processes with desirable features and tractability.     

Heuristics and metaheuristics for the maximum diversity problem

This paper presents extensive computational experiments to compare 10 heuristics and 20 metaheuristics for the maximum diversity problem (MDP). This problem consists of selecting a subset of maximum diversity from a given set of elements. It arises in a wide range of real-world settings and we can find a large number of studies, in which heuristic and metaheuristic methods are proposed. However, probably due to the fact that this problem has been referenced under different names, we have only found limited comparisons with a few methods on some sets of instances. This paper reviews all the heuristics and metaheuristics for finding near-optimal solutions for the MDP. We present the new benchmark library MDPLIB, which includes most instances previously used for this problem, as well as new ones, giving a total of 315. We also present an exhaustive computational comparison of the 30 methods on the MDPLIB. Non-parametric statistical tests are reported in our study to draw significant conclusions.