Novel methyl helianthrones as photosensitizers: synthesis and biological evaluation

A combination of light, oxygen and a photosensitizer is used to induce death of cancer cells by photodynamic therapy. In this study, we have synthesized several new methyl helianthrone derivatives and compared their phototoxicity with that of hypericin. In contrast to hypericin, methyl helianthrones are soluble in aqueous solutions and have a broad range of light absorbance, which allows the use of polychromatic light. Structural modifications of methyl helianthrone demonstrated that substitution of hydrogen atoms of methyl helianthrone at Positions 2 and 5 with Br atoms or methylation of its phenolic hydroxyls, significantly increases the corresponding singlet oxygen quantum yield and their phototoxicity toward alphaT3-1, M2R and LNCaP cells. The phototoxicity of some of these compounds was similar to that of hypericin. Methyl helianthrones, like hypericin, accumulated mainly in the perinuclear region as evident by confocal microscopy. Irradiation of cells pretreated with methyl helianthrone derivatives generates intracellular reactive oxygen species and lipid free radicals, as shown by a fluorescentic probe and electron paramagnetic resonance methods, respectively. The phototoxicity of these methyl helianthrones as well as their ability to oxidize membrane lipids were significantly decreased on addition of specific Type-II inhibitors, suggesting the involvement of singlet oxygen as the main oxidant.     

Reverse self-assembly: (111)-oriented gold crystallization at alkylthiol monolayer templates

It has long been known that thiol-terminated molecules self-assemble as commensurate monolayers on Au(111) surfaces. By spreading floating octadecanethiol monolayers on aqueous solutions of chloroauric acid (HAuCl4) and using x rays to reduce the gold ions as well as to probe the structure, we have observed the nucleation of (111)-oriented Au nanoparticles at thiol surfaces. This process may be similar to the formation of biogenic gold by bacteria. The thiol monolayer acts as a "soft template," changing its structure as Au crystals form so that there is a sqrt[3]×sqrt[3] commensurate relationship.     

Sonochemical effectiveness factor (eUS) in the reactors for wastewater treatment by sono-Fenton oxidation: Novel considerations

A comprehensive algorithm was recently proposed for calculation of the sonochemical effectiveness factor and wastewater treatment modeling. The presented approach implies that ultrasound is an auxiliary source of free radicals in Fenton type reactions; introduction of ultrasound represents an enhancement of pollutant degradation rates. The sonochemical effectiveness factor was introduced in kinetic models as the e_US factor (Gr?i? et al., 2012 [1]). As a substantial follow-up, this study presents novel considerations. The e_US factor was modeled as a function of employed frequency, actual cavitation-related power intensity of ultrasound and a portion of the cavitationally active zone, i.e. dimensionless active volume. The effect of temperature was disregarded in the present model considerations. Cavitationally active zone in reactors was determined based on the erosion of aluminum foil, resulting in cone-shaped space arising from transducer.In the present study, sonochemical treatment of industrial wastewater containing HCOONa as organic pollutant was performed using different equipment: ultrasonic baths (UB1, UB2 and UB3), cylindrical reactor with homogenizer (HCR) and three-frequency hexagonal cell, i.e. ultrasonic pilot reactor prototype (PP). Explored frequency range was from 20 to 120 kHz. Homogeneous and heterogeneous Fenton-type sonochemical processes, US/Fe(II)(FeSO₄,aq.)/H₂O₂ and US/Fe(II)(steel-plate)/H₂O₂, respectively, applied to industrial wastewater were investigated in terms of mineralization kinetics. Newly modeled e_US factor was introduced in corresponding kinetic models and the overall model was validated. Kinetic parameters of Fenton process were treated as independent of ultrasound, since e_US factor consists of cavitation-related phenomena responsible for the mineralization rate enhancement. In average, a 21% increase of mineralization efficiency was achieved using a single frequency, while more than 70% increase can be achieved by combining 20, 68 and 120 kHz in PP.     

Barzilai–Borwein method with variable sample size for stochastic linear complementarity problems

A smoothing method for solving stochastic linear complementarity problems is proposed. The expected residual minimization reformulation of the problem is considered, and it is approximated by the sample average approximation (SAA). The proposed method is based on sequential solving of a sequence of smoothing problems where each of the smoothing problems is defined with its own sample average approximation. A nonmonotone line search with a variant of the Barzilai–Borwein (BB) gradient direction is used for solving each of the smoothing problems. The BB search direction is efficient and low cost, particularly suitable for nonmonotone line search procedure. The variable sample size scheme allows the sample size to vary across the iterations and the method tends to use smaller sample size far away from the solution. The key point of this strategy is a good balance between the variable sample size strategy, the smoothing sequence and nonmonotonicity. Eventually, the maximal sample size is used and the SAA problem is solved. Presented numerical results indicate that the proposed strategy reduces the overall computational cost.     

Thermal dileptons in high-energy nuclear collisions

Clear signs of excess dileptons above the known sources have been found at the SPS for a long time. However, a real clarification of these observations was only recently achieved by NA60, measuring dimuons with unprecedented precision in 158A GeV In-In collisions. The excess mass spectrum in the region is consistent with a dominant contribution from π⁺π⁻→ρ→μ⁺μ⁻ annihilation. The associated ρ spectral function shows a strong broadening, but essentially no shift in mass. In the region , the excess is found to be prompt, not due to enhanced charm production. The inverse slope parameter associated with the transverse momentum spectra rises with mass up to the ρ, followed by a sudden decline above. While the initial rise, coupled to a hierarchy in hadron freeze-out, points to radial flow of a hadronic decay source, the decline above signals a transition to a low-flow source, presumably of partonic origin. The mass spectra show a steep rise towards low masses characteristic of Planck-like radiation. The polarization of the excess referred to the Collins Soper frame is found to be isotropic. All observations are consistent with a global interpretation of the excess as thermal radiation. We conclude with a short discussion of a possible link to direct photons.     

Design, synthesis and biological evaluation of non-natural modulators of quorum sensing in Pseudomonas aeruginosa

Many species of bacteria employ a mechanism of intercellular communication known as quorum sensing which is mediated by small diffusible signalling molecules termed autoinducers. The most common class of autoinducer used by Gram-negative bacteria are N-acylated-L-homoserine lactones (AHLs). Pseudomonas aeruginosa is a clinically important bacterium which is known to use AHL-mediated quorum sensing systems to regulate a variety of processes associated with virulence. Thus the selective disruption of AHL-based quorum sensing represents a strategy to attenuate the pathogenicity of this bacterium. Herein we describe the design, synthesis and biological evaluation of a collection of structurally novel AHL mimics. A number of new compounds capable of modulating the LasR-dependent quorum sensing system of P. aeruginosa were identified, which could have value as molecular tools to study and manipulate this signalling pathway. Worthy of particular note, this research has delivered novel potent quorum sensing antagonists, which strongly inhibit the production of virulence factors in a wild type strain of this pathogenic bacterium.     

Characterization analysis of raw and pyrolyzed plane tree seed (Platanus orientalis L.) samples for its application in carbon capture and storage (CCS) technology

Journal of Thermal Analysis and Calorimetry - Raw and pyrolyzed samples of the plane tree seeds (PTS) were tested by various advanced analytical techniques including simultaneous TG-DSC technique,...     

Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions

Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions.