Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids

In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r²) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd.     

Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

Critical Point Theorems and Applications to Differential Equations

This paper contains a generalization of the well-known Palais-Smale and Cerami compactness conditions. The compactness condition introduced is used to prove some general existence theorems for critical points. Some applications are given to differential equations.     

Influence of oxidation time on semiconductive behaviour of thermally grown oxide films on AISI 304L

The oxide films formed on AISI 304L stainless steel at 300 °C in the oxidation time range between 2 and 4 h have been studied by photoelectrochemistry. Photocurrents were investigated as a function of the wavelength of the incident light and the electrode potential. The investigation allowed the determination of the semiconductive properties of the oxides. The oxide films showed n-type behaviour. A duplex structure of the oxide films has been suggested on the basis of the photocurrent spectra, with an internal oxide layer having an optical gap (E_g2 = 2.16-2.3 eV) depending on the applied potential and oxidation time, higher to that of the external oxide layer (E_g1 ≈ 1.9 eV). Significant variations in the amplitude of the photocurrent were detected as a function of the applied potential and the oxidation time.     

Diagramme polythermique du systeme ternaire H2O—Al(NO3)3—Mg(NO3)2

The solid—liquid equilibria of the ternary system H₂O—Al(NO₃)₃—Mg(NO₃)₂ were studied at –30, –20, –10 and 0°C by using a synthetic method which allows to detemine all the characteristic points of isothermal sections. The stable solid phases which appear are respectively: ice, Al(NO₃)₃·9H₂O, Mg(NO₃)₂·9H₂O and Mg(NO₃)₂·6H₂O. Neither double salts nor mixed crystals are observed in the temperature and composition field studied. Polytherm diagram layout show two invariant transformations correspond with an eutectic point and a peritectic point.This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis of a new class of uridine phosphorylase inhibitors

A new series of potent uridine phosphorylase inhibitors have been prepared from barbituric acid. Among them, 1-[(2-hydroxyethoxy)methyl]-5-)(m--benzyloxy)benzylbarbituric acid ( 37 , BBBA) is the most promising having a K_i value of 1.1 ± 0.2 nM with uridine phosphorylase from human liver. The new inhibitors are easily synthesized and are better inhibitors of human uridine phosphorylase than their uracil counterparts.     

The Problem of Capacity Addition in Multi-user Elastic Demand Communication Networks

In this paper we consider some properties on prices under flow control in a network that is to be shared by noncooperative users. Each user is faced with an optimization problem which is formulated as the minimization of its own criterion subject to constraint on the flows of the other users. The operating points of the network are the Nash equilibria of the underlying routing game. Our objective is to study the behavior of prices of all users when the network designer needs to allocate capacities to network links. For parallel links topologies, we show that degradation of the performances such as prices will not take place, as well as the users may find it beneficial to improve their requests