Efficient syntheses of 3-phosphorylquinolin-4-ones and 3-phosphoryl-1,8-naphthyridin-4-ones

A series of 3-diethoxyphosphorylquinolin-4-ones and 3-diethoxyphosphoryl-1,8-naphthyridin-4-ones containing various substituents at N-1 and C-7 was synthesized in a four-step reaction sequence starting from readily available ethyl 2-chlorobenzoates or ethyl 2-chloronicotinates and diethyl methylphosphonate. Selected quinolinone and naphthyridinone products were transformed into free mono and diacids.     

Application of ultra-performance columns in high-performance liquid chromatography for determination of albendazole and its metabolites in turkeys

Methods for determination of albendazole (ALB), albendazole sulfoxide (SOX) and albendazole sulfone (SON) in turkey blood plasma, using high‐performance liquid chromatography (HPLC) with fluorescence detection, were developed. Moreover, comparison of HPLC columns with ultra‐performance liquid chromatography (UPLC) columns was performed. Albendazol was administered orally in 5‐week‐old birds (n = 18) at a dose of 25 mg/kg b.w. Accuracy and precision of the developed method were satisfactory and stability studies showed acceptable variation (below 15%) in ALB, SOX and SON concentrations when the samples were stored at –75°C for 15 days. UPLC® columns gave higher peaks from typical HPLC columns retaining high quality of analysis. Pharmacokinetic analysis indicated quick elimination of ALB from turkey blood plasma. The mean residence time of SON was at least two times longer than that of SOX and four times longer than that of ALB. The elimination half‐lives for ALB, SOX and SON were 0.7 ± 0.27, 5.37 ± 6.03, 9.17 ± 5.12 h, respectively. The obtained results indicate that the described method allows for precise determination of albendazole and its metabolites in turkey plasma. Moreover, using UPLC columns in HPLC apparatus results in higher sensitivity as compared with the classical HPLC columns. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and photochemical characteristics of novel tribenzoporphyrazines possessing peripherally annulated tetrahydrodiazepine and diazepine rings

Novel tribenzoporphyrazines possessing peripherally annulated tetrahydrodiazepine and diazepine rings were synthesized and characterized, and the substituent effects on their absorption spectra in various solvents and on singlet oxygen generation were studied. Solvatochromic effects of tribenzoporphyrazines dissolved in a range of protic and aprotic solvents were evaluated by monitoring the changes in the UV-Vis spectra. The correlation between the Q-band shift towards longer wavelengths and the refractive index of the solvent indicated that the solvatochromic effects are mainly a result of solvation rather than coordination processes. The potential photosensitizing activity of novel tribenzoporphyrazines was evaluated by measuring the ability of singlet oxygen production, which is the result of the interaction between an activated photosensitizer and oxygen. This experiment proves promising photosensitizing activity of novel styryldiazepinotribenzoporphyrazine, which is an efficient singlet oxygen generator with a Φ_Δ value of 0.44, although this value is a little lower than that of zinc phthalocyanine.     

Multi-attribute aggregation operators

This paper deals with the idea of aggregation. A new, enlarged notion of aggregation operator is given, along with a classification of classical properties into some main groups. The concept of multi-attribute aggregation operator, which incorporates many classical aggregation methods, is provided. An extension of different properties to multi-attribute aggregation operators is proposed.     

On solving the dual for portfolio selection by optimizing Conditional Value at Risk

This note is focused on computational efficiency of the portfolio selection models based on the Conditional Value at Risk (CVaR) risk measure. The CVaR measure represents the mean shortfall at a specified confidence level and its optimization may be expressed with a Linear Programming (LP) model. The corresponding portfolio selection models can be solved with general purpose LP solvers. However, in the case of more advanced simulation models employed for scenario generation one may get several thousands of scenarios. This may lead to the LP model with huge number of variables and constraints thus decreasing the computational efficiency of the model. To overcome this difficulty some alternative solution approaches are explored employing cutting planes or nondifferential optimization techniques among others. Without questioning importance and quality of the introduced methods we demonstrate much better performances of the simplex method when applied to appropriately rebuilt CVaR models taking advantages of the LP duality.     

Δ(1232) axial charge and form factors from lattice QCD

We present the first calculation on the Δ axial?vector and pseudoscalar form factors using lattice QCD. Two Goldberger-Treiman relations are derived and examined. A combined chiral fit is performed to the nucleon axial charge, N to Δ axial transition coupling constant and Δ axial charge.     

The observable pressure of light in dielectric fluids

By considering a perfect reflector submerged in a dielectric fluid, we show that the Minkowski formulation describes the optical momentum transfer to submerged objects. This result is required by global energy conservation, regardless of the phase of the reflected wave. While the electromagnetic pressure on a submerged reflector can vary with phase of the mirror reflection coefficient between twice the Abraham momentum and twice the Minkowski momentum, the Minkowski momentum is always restored due to the additional pressure on the dielectric surface. This analysis also gives further evidence for use of the Minkowski stress tensor at the boundary of a dielectric interface, which has been the subject of a long-standing debate in physics and the source of uncertainty in the modeling of optical forces on submerged particles.     

Thermostability of glucose oxidase in silica gel obtained by sol-gel method and in solution studied by fluorimetric method

The thermostability of glucose oxidase entrapped in silica gel obtained by sol-gel method was studied by thermostimulated fluorescence of FAD at pH 5 and 7 and compared with that of the native enzyme in the solution and at the presence of ethanol. The unfolding temperatures were found to be lower for the enzyme immobilised in gel as compared with the native enzyme but higher as for the enzyme at the presence of ethanol. In gel, the thermal denaturation of glucose oxidase is independent on pH while in solution the enzyme is more stable at pH 5. The investigation the enzyme in different environment by steady-state fluorescence of FAD and tryptophan, synchronous fluorescence and time-resolved fluorescence of tryptophan indicates that the state of the molecule (tertiary structure and molecular dynamics) is different in gel and in solution. The ethanol produced during gel precursor hydrolysis is not the main factor influencing the thermostability of the enzyme but more important are interactions of the protein with the gel lattice.     

Global versus local QSPR models for persistent organic pollutants: balancing between predictivity and economy

Experimentally determined data on the key physicochemical parameters for halogenated congeners of persistent organic pollutants (POPs) are available only for a limited number of compounds. In the absence of experimental data, a range of computational methods can be applied to characterize those species for which experimental data is not available. One of the techniques widely used in this context is quantitative structure–property relationships (QSPR) approach. There are two ways to develop the QSPR models: using a more complex global model or fitting a simple local model that covers a specific class of chemically related compounds. The essence of the study was to investigate, if local models have significantly better explanatory and predictive ability than global models with wider applicability domains. Based on the obtained results, we concluded that whenever global models fulfill all quality recommendations by OECD, they would be applied in practice as more efficient ones in state of more time consuming procedure of modeling the particular groups of POPs one-by-one. On the contrary, local models are applicable to solve specific problems (i.e., related to only one group of POPs), when high-quality experimental data are available for a sufficient number of training and validation compounds.     

Catalytic residues in hydrolases: analysis of methods designed for ligand-binding site prediction

The comparison of eight tools applicable to ligand-binding site prediction is presented. The methods examined cover three types of approaches: the geometrical (CASTp, PASS, Pocket-Finder), the physicochemical (Q-SiteFinder, FOD) and the knowledge-based (ConSurf, SuMo, WebFEATURE). The accuracy of predictions was measured in reference to the catalytic residues documented in the Catalytic Site Atlas. The test was performed on a set comprising selected chains of hydrolases. The results were analysed with regard to size, polarity, secondary structure, accessible solvent area of predicted sites as well as parameters commonly used in machine learning (F-measure, MCC). The relative accuracies of predictions are presented in the ROC space, allowing determination of the optimal methods by means of the ROC convex hull. Additionally the minimum expected cost analysis was performed. Both advantages and disadvantages of the eight methods are presented. Characterization of protein chains in respect to the level of difficulty in the active site prediction is introduced. The main reasons for failures are discussed. Overall, the best performance offers SuMo followed by FOD, while Pocket-Finder is the best method among the geometrical approaches.