Theoretical study on the gas‐phase reactivity of halogenated alkylperoxyl radicals toward alkenes

The electrophilic additions of hydroperoxyl (HO ${}_{\text{2}}^{\text{⋅}}$), alkylperoxyl (RO ${}_{\text{2}}^{\text{⋅}}$), and halogenated alkylperoxyl radicals to ethylene were studied using the AM1 and PM3 semiempirical MO methods at the SCF/UHF level. Reactantlike transition states were predicted for the title additions. The AM1 activation enthalpies (ΔH ${}_{\text{f}}^{\text{*}}$) were found to be increased in the order HO ${}_{\text{2}}^{\text{⋅}}$<CH₃O ${}_{\text{2}}^{\text{⋅}}$<C₂H₅O ${}_{\text{2}}^{\text{⋅}}$<i‐C₃H₇O ${}_{\text{2}}^{\text{⋅}}$. The reactivity of an alkylperoxyl radical toward ethylene was found to be increased as the degree of halogen substitution on the alkyl group increased. A good correlation was established between ΔH ${}_{\text{f}}^{\text{*}}$ and the Taft polar substituent constants, σ*. The Evans–Polanyi correlation between ΔH ${}_{\text{f}}^{\text{*}}$ and ΔH ${}_{\text{r}}^{\text{°}}$ was justified and the validity of the Hammond postulate was indicated. The calculated results were compared with the available experimental findings. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 273–283, 1999     

An optimal type II fuzzy sliding mode control design for a class of nonlinear systems

This study deals with the problem of controlling a class of uncertain nonlinear systems in the presence of external disturbances. To achieve this goal, a new Optimal Type-2 Fuzzy Sliding Mode Controller (OT2FSMC) is introduced. In the proposed controller, a novel heuristic algorithm, namely particle swarm optimization with random inertia weight (RNW–PSO), is employed. To achieve an optimal performance, the parameters of the proposed controller as well as the input and output membership functions are optimized simultaneously by RNW–PSO. The globally asymptotic stability of the closed-loop system is mathematically proved. Finally, this method of control is applied to the inverted pendulum system as a case study. Simulation results show the system performance is desirable.     

A Novel Strategy for Determination of Paracetamol in the Presence of Morphine Using a Carbon Paste Electrode Modified with CdO Nanoparticles and Ionic Liquids

A voltammetric sensor for determination of paracetamol in the presence of morphine is described for the first time. The synthesized CdO nanoparticles were characterized with different methods such as scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The paracetamol and morphine peaks are separated ca. 0.37 and 0.65 V, respectively; hence paracetamol can be analysed in the presence of morphine and more than 21 times of the current excess of paracetamol. The detection limits for paracetamol and morphine were 0.07 and 0.1 μM, respectively. The sensor has been successfully applied for the assay of the above compounds in real samples.     

A cellular uptake and cytotoxicity properties study of gallic acid-loaded mesoporous silica nanoparticles on Caco-2 cells

In this study, the effects of intracellular delivery of various concentrations of gallic acid (GA) as a semistable antioxidant, gallic acid-loaded mesoporous silica nanoparticles (MSNs-GA), and cellular uptake of nanoparticles into Caco-2 cells were investigated. MSNs were synthesized and loaded with GA, then characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, N₂ adsorption isotherms, X-ray diffraction, and thermal gravimetric analysis. The cytotoxicity of MSNs and MSNs-GA at low and high concentrations were studied by means of 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) test and flow cytometry. MSNs did not show significant toxicity in various concentrations (0–500 μg/ml) on Caco-2 cells. For MSNs-GA, cell viability was reduced as a function of incubation time and different concentrations of nanoparticles. The in vitro GA release from MSNs-GA exhibited the same antitumor properties as free GA on Caco-2 cells. Flow cytometry results confirmed those obtained using MTT assay. TEM and fluorescent microscopy confirmed the internalization of MSNs by Caco-2 cells through nonspecific cellular uptake. MSNs can easily internalize into Caco-2 cells without deleterious effects on cell viability. The cell viability of Caco-2 cells was affected during MSNs-GA uptake. MSNs could be designed as suitable nanocarriers for antioxidants delivery.     

A Simple Synthesis of Stable Phosphoranes Derived from Imidazole Derivatives

Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, in the presence of strong NH-acids, such as imidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, benzimidazole, and 5,6-dimethylbezimidazole. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group.     

A Simple Synthesis of Stable Phosphorus Ylides from Indole and Some of Its Derivatives

Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of strong NH acids, such as indole and 2-methyl indole, 3-methyl indole, and 5-boromo indole. These stable ylides exist in a solution as a mixture of two geometrical isomers as a result of the restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group.