Crude peroxidase from onion solid waste as a tool for organic synthesis. Part II: oxidative dimerization-cyclization of methyl p-coumarate, methyl caffeate and methyl ferulate

The ability of a crude onion peroxidase preparation to act as a biocatalyst for the oxidative dimerization-cyclization of methyl p-coumarate, methyl caffeate and methyl ferulate is presented. The products of the reaction have been fully characterized and were found to possess potent antioxidant activity in a ferric reducing antioxidant power (FRAP) assay.     

Design,synthesis, and cytotoxic activity evaluation of new linear pyranoxanthone aminoderivatives

With the aim of enlightening some structure‐activity correlation within the pyranoxanthenone series, we have designed and synthesized a number of new 5‐aminosubstituted pyrano[3,2‐b]xanthen‐6‐ones bearing various 12‐substituents. In vitro cytotoxic potencies of the new derivatives toward the murine leukemia L1210 cell line, human colorectal adenocarcinoma (HT‐29), and human uterine sarcoma (MES‐SA and its 100‐fold resistant to doxorubicin variant MES‐SA/Dx5) cell lines, are described and compared with that of reference drugs. Among the studied compounds, those possessing a second aminosubstituted side‐chain exhibit interesting cytotoxic activity against the solid tumor cell lines, and they retain activity against the multidrug resistant MES‐SA/Dx5 subline. Their selective effect on a phase of the cell cycle was evaluated using HT‐29 cells providing evidence that the compounds induce a G0/G1 arrest. J. Heterocyclic Chem., (2011).     

Enhanced photon harvesting in silicon multicrystalline solar cells by new lanthanide complexes as light concentrators

Four europium complexes with enhanced luminescent properties have been synthesized. Thin transparent films of the complexes were prepared on glass panes and then were examined as efficient luminescent solar concentrators for full spectrum utilization in crystalline silicon photovoltaic cells. The complexes could behave as efficient solar concentrators since they absorb UV light, where the spectral response of the crystalline silicon solar cells is low and they emit at 615 nm where the spectral response is maximum. The glass panes covered with europium complexes act as planar waveguides of the emitted light that is collected by the solar cells, which are attached to the edges of the solar concentrators. The europium complexes as solar concentrators were examined in terms of the optimum concentrations and the number of coatings, which were determined in order to evaluate the maximum performance of the solar cells. The case of multiple glass panes with europium complexes was also examined while a 28% maximum increase in the photocurrent was finally established.     

Structure of bottle-brush brushes under good solvent conditions: a molecular dynamics study

We report a simulation study for bottle-brush polymers grafted on a rigid backbone. Using a standard coarse-grained bead-spring model extensive molecular dynamics simulations for such macromolecules under good solvent conditions are performed. We consider a broad range of parameters and present numerical results for the monomer density profile, density of the untethered ends of the grafted flexible backbones and the correlation function describing the range that neighboring grafted bottle-brushes are affected by the presence of the others due to the excluded-volume interactions. The end beads of the flexible backbones of the grafted bottle-brushes do not access the region close to the rigid backbone due to the presence of the side chains of the grafted bottle-brush polymers, which stretch the chains further in the radial directions. Although a number of different correlation lengths exist as a result of the complex structure of these macromolecules, their properties can be tuned with high accuracy in good solvents. Moreover, qualitative differences with 'typical' bottle-brushes are discussed. Our results provide a first approach to characterizing such complex macromolecules with a standard bead-spring model.     

Synthesis and antiviral activity evaluation of some novel acyclic C-nucleosides

The preparation of novel 5-amino or 7-hydroxy substituted pyrazolo[4,3-b]pyridine and pyrazolo[3,4-c]pyridine acyclic C-nucleosides is described. Their synthesis was carried out by condensation of suitably substituted lithiated picolines with 2-benzyloxyethoxymethylchloride followed by pyrazole ring annulation. The compounds were evaluated for their antiviral activity against a wide panel of viruses, but were found inactive at subtoxic concentrations.     

Synthesis and Characterization of MoFe3S4 and Mo2Fe2S4 Single Cubanes

The synthesis of multimetallic M/S clusters by the reductive coupling of dimeric building blocks appears to be of general utility. In this paper we describe the synthesis and characterization of new single cubanes with cores such as [Mo₂Fe₂S₄]²⁺ and [MoFe₃S₄]^3+,2+.     

The informational value of employee online reviews

This paper investigates the informational value of online reviews posted by employees for their employer, a rather untapped source of online information from employees, using a sample of 349,550 reviews from 40,915 UK firms. We explore this novel form of electronic Word-of-Mouth (e-WOM) from different perspectives, namely: (i) its information content as a tool to identify the drivers of job satisfaction/dissatisfaction, (ii) its predictive ability on firm financial performance and (iii) its operational and managerial value. Our approach considers both the rating score as well as the review text through a probabilistic topic modeling method, providing also a roadmap to quantify and exploit employee big data analytics. The novelty of this study lies in the coupling of structured and unstructured data for deriving managerial insights through a battery of econometric, financial and operational research methodologies. Our empirical analyses reveal that employee online reviews have informational value and incremental predictability gains for a firm's internal and external stakeholders. The results indicate that when models integrate structured and unstructured big data there are leveraged opportunities for firms and managers to enhance the informativeness of decision support systems and in turn, gain competitive advantage.     

Site percolation and isoperimetric inequalities for plane graphs

We use isoperimetric inequalities combined with a new technique to prove upper bounds for the site percolation threshold of plane graphs with given minimum degree conditions. In the process we prove tight new isoperimetric bounds for certain classes of hyperbolic graphs. This establishes the vertex isoperimetric constant for all triangular and square hyperbolic lattices, answering a question of Lyons and Peres. We prove that plane graphs of minimum degree at least 7 have site percolation threshold bounded away from 1/2, which was conjectured by Benjamini and Schramm, and make progress on a conjecture of Angel, Benjamini, and Horesh that the critical probability is at most 1/2 for plane triangulations of minimum degree 6. We prove additional bounds for stronger minimum degree conditions, and for graphs without triangular faces.     

Performance of different separation methods interfaced in the same MS-reflection TOF detector: a comparison of performance between CE versus HPLC for biomarker analysis

One of the aims in the field of proteomics is the identification of a protein or polypeptide, or a range of these compounds, that could provide pre-symptomatic indication of the onset of a disease. A number of analytical techniques have been employed to try and achieve this end. These techniques have been applied to the complete range of body fluids and tissues that are readily available from clinical studies. Of these sample sources, the urinary low molecular weight peptidome has been shown to reflect changes in the health status of the individual. The alterations that occur in the polypeptide make up of urine, which reflect changes in biological status, are known as biomarkers. To be able to determine these changes no single technique has emerged that can cope with detecting the large number of peptides present and quantifying them over the wide concentration range they exist in. In this investigation, we made use of a single reflectron time of flight (RTOF)-MS analyser to which we first connected a CE system and then a nanoflow HPLC. Two pooled male and female standard urine samples were compared on these systems. Both techniques had similar results in terms of number of peptides detected and the mass range the peptides were detected over. The major differences in terms of biomarker research were the ability in CE to calibrate the migration time of the peptides to allow comparison between samples. In addition, CE was shown not to suffer from carry over from previous samples as was seen in the LC analysis.     

Water-soluble hydrogen-bonding interpolymer complex formation between poly(ethylene glycol) and poly(acrylic acid) grafted with poly(2-acrylamido-2-methylpropanesulfonic acid)

Comb-type copolymers of poly(acrylic acid) grafted with poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPSA) side chains form with poly(ethylene glycol), at low pH, water-soluble hydrogen-bonding interpolymer complexes. Turbidimetry, viscometry, and dynamic light scattering measurements suggest that compact, negatively charged, colloidal nanoparticles are formed at pH<3.75. The influence of the structure of the graft copolymers and of the ionic strength of the solution on the size of these nanoparticles was investigated. It was found that their hydrodynamic radius decreases by increasing the molecular mass of the PAMPSA side chains of the graft copolymer and increases with increasing the ionic strength of the solution.