Oxidation of pentan-2-ol – Part I: Theoretical investigation on the decomposition and isomerization reactions of pentan-2-ol radicals

Theoretical investigations on the kinetics of pentan-2-ol radical decomposition and isomerization reactions have been carried out in this work, together with the thermochemistry data calculations for important species involved in the reaction process. The B2PLYPD3/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hindered rotor treatment for lower frequency modes. Single-point energies of all species are determined at the ROCCSD(T) level using the cc-PVQZ and cc-pVTZ which were extrapolated to the complete basis set limit (CBS). RRKM/Master Equation has been solved to calculate the pressure- and temperature-dependent rate coefficients for all channels in the pressure range of 0.01–100 atm over 300–2000 K. Pressure and temperature dependent branching fractions of key species produced from different pentan-2-ol radicals shows that 1- and 2-pentene are important bimolecular products. The kinetics and thermochemistry data for the title reactions has been used in the part II of this work for model development for pentan-2-ol oxidation.     

Oxidation of di-n-propyl ether: Characterization of low-temperature products

The oxidation of di-n-propyl-ether (DPE) was performed in a jet-stirred reactor at 1 and 10 atm, at residence times of 1 and 0.7 s, respectively, and initial fuel concentrations of 5000 and 1000 ppm at 1 and 10 atm, respectively. Atmospheric pressure experiments were used for characterization of cool flame products. The 10 atm experiment provided KHPs profile vs. temperature and mole fraction profiles of stable species which were obtained through sonic probe sampling, gas chromatography, Fourier transform infrared spectrometry analyses. High resolution mass spectrometry analyses (HRMS) with syringe direct injection or ultra-high-pressure liquid chromatography coupling was used to characterize hydroperoxides (C₃H₈O₂, C₆H₁₄O₃), diols (C₆H₁₄O₃), ketohydroperoxides (C₆H₁₂O₄), carboxylic acids, and highly oxygenated molecules (C₆H₁₂O₆, C₆H₁₂O₈) resulting from up to four O₂ additions on fuel's radicals. Heated electrospray and atmospheric pressure chemical ionizations (HESI and APCI) were used in positive and negative mode. Whereas the CH₂ groups neighboring the ether function are the most favorable sites for H-atom abstraction reactions, speciation indicated that other sites can react by metathesis forming a large pool of intermediates. Our kinetic reaction mechanism represents the experimental data for most of the stable species but need to be expended for simulating the formation of newly detected species.     

Simple and Sensitive Spectrofluorimetric Method for the Determination of Oseltamivir Phosphate in Capsules Through Derivatization with Fluorescamine

A new, simple and sensitive spectrofluorimetric method has been developed for the determination of oseltamivir phosphate (OSP) in capsules. The method is based on the reaction between oseltamivir and fluorescamine in borate buffer solution of pH 8.50 to give highly fluorescent derivatives that are measured at 483 nm using an excitation wavelength of 381. The different experimental parameters effecting the development and stability of the reaction product were carefully studied and optimized. The fluorescence intensity concentration plot is rectilinear over the range 50–450 ng mL⁻¹ with a lower detection limit (LOD) of 1.219 ng mL⁻¹ and limit of quantitation (LOQ) of 4.064 ng mL⁻¹. Selectivity was validated by subjecting stock solution of OSP to acidic, basic, oxidative, and thermal degradation. No interference was observed from excipients present in formulations. The developed method was successfully applied to determination of the drug in capsules. The mean % recovery (n = 6) was 100.08. The results obtained were in good agreement with those obtained using a reported spectrophotometric method.     

An approximation for kanban controlled assembly systems

An approximation is proposed to evaluate the steady-state performance of kanban controlled two-stage assembly systems. The development of the approximation is as follows. The considered continuous-time Markov chain is aggregated keeping the model exact, and this aggregate model is approximated replacing some state-dependent transition rates with constant rates. The approximate aggregate model is, then, decomposed into submodels and a product-form steady-state distribution is obtained for each submodel. Finally, the submodels are combined in such a way that the size of the problem becomes independent of the number of kanbans. This leads to the computational advantage in solving the combined model using numerical matrix-geometric solution algorithms. Numerical comparisons of the combined model with simulation, exact model, approximate aggregate model and an approximation in the literature show that the proposed approximation performs well in terms of accuracy and computational burden.     

The stochastic transportation problem with single sourcing

We propose a branch-and-price algorithm for solving a class of stochastic transportation problems with single-sourcing constraints. Our approach allows for general demand distributions, nonlinear cost structures, and capacity expansion opportunities. The pricing problem is a knapsack problem with variable item sizes and concave costs that is interesting in its own right. We perform an extensive set of computational experiments illustrating the efficacy of our approach. In addition, we study the cost of the single-sourcing constraints.     

Undifferentiated (embryonal) sarcoma of the liver (USL): MRI findings including dynamic gadolinium enhancement

We report the MR appearance of undifferentiated (embryonal) sarcoma of the liver (USL) in a 13-year-old female who presented with a 1-year history of intermittent abdominal pain, weight loss, and fatigue. The tumor was a large, solitary, well-defined focal mass lesion with multiple cystic spaces, septations, and substantial central necrosis.     

Hepatic nodules in liver transplantation candidates: MR imaging and underlying hepatic disease

OBJECTIVE: To assess by MR imaging the frequency of hepatic nodules in patients waiting on the liver transplant list and to determine whether certain underlying hepatic diseases were more often associated with the development of such hepatic nodules. MATERIAL AND METHODS: We reviewed the MR and clinical records in all patients seen by the liver transplant service at our center since its inception in January 1998 until September 2002. A total of 371 patients (207 men and 164 women, age range 18-68 years, mean 45 years) were included in the study. The presence of hepatic nodules, size, number and underlying hepatic diseases were determined in all patients. Magnetic resonance imaging was performed on a 1.5-T MR imager using T1-weighted, T2-weighted and multi-phase gadolinium-enhanced sequences. Odds ratio (OR) and 95% confidence intervals (CIs) were computed to evaluate the association between the underlying hepatic disease and the development of hepatic nodule. RESULTS: Among 371 liver transplantation candidates, the most common underlying hepatic disease was hepatitis C virus (HCV) infection, either alone (n=93; 25%) or associated with other hepatic diseases (n=40; 10.8%). Of all patients, 33 (8.9%) had regenerative nodules (RNs), 40 (10.7%) dysplastic nodules (DNs) and 57 (15.3%) hepatocellular carcinomas (HCCs). Hepatocellular carcinoma was observed in 35.3% of patients with HCV infection and alcohol abuse combined, 24.5% with cryptogenic cirrhosis, 25% with hemochromatosis and 19% with alcohol abuse. Patients who had either DNs or HCC were 2.5 times more likely to have either alcohol abuse or HCV, alone or combined, as the substrate of their liver disease (OR 2.54, 95% CI 1.56-4.13). Our data suggest a supra-additive interaction between HCV infection and ethanol in their association with MR imaging detected lesions. CONCLUSION: Patients with cryptogenic cirrhosis, alcohol abuse, HCV infection (alone or combined) and hemochromatosis had the greatest likelihood of having HCC, with the combination of HCV infection and alcohol abuse having the highest of all.     

Energy absorption buildup factors of some potential bioactive compounds in the energy region 0.015–15 MeV

Kinetic energy released per unit mass relative to air and energy absorption buildup factors has been calculated for some potential bioactive compounds in the energy region of 0.015–15?MeV. The bioactive compounds of 1-aryl-3-dibenzylamino-propane-1-on hydrochloride type Mannich bases were used in this work. Aryl part was changed as C₆H₅ (1), 4-CH₃C₆H₄ (2), C₄H₃S-2-yl (3), 4-FC₆H₄ (4), 4-BrC₆H₄ (5), 4-ClC₆H₄ (6), and 4-NO₂C₆H₄ (7). The energy absorption buildup factors have been calculated for penetration depth of 40 mean free paths. It is observed that kinetic energy released per unit mass relative to air depends on the photon energy and chemical content of compounds. The compounds with least mean atomic number possess the maximum value of energy absorption buildup factors. Also, the energy absorption buildup factors are found the highest in intermediate energy, whereas the lowest in low as well as high energies.     

EPR study of gamma-irradiated 2-Bromo-4′-methoxyacetophenone single crystals

The gamma-irradiated single crystals of 2-Bromo-4′-methoxyaceto-phenone (2B4MA) were investigated using electron paramagnetic resonance (EPR) technique. Density-functional theory calculations were employed to investigate and identify the radicals that have been assumed to be formed upon irradiation of 2B4MA single crystals. The EPR spectra of 2B4MA were recorded at different orientations in the magnetic field at room temperature. Taking into account the chemical structure and experimental spectra of irradiated single crystal of 2B4MA, it was assumed that at least two different radicals were produced in the sample. Following this assumption, six possible radicals were modeled and EPR parameters were calculated by using the DFT, B3LYP/6-311+G(d), for the modeled radicals individually. The calculated hyperfine coupling constants and g-tensors were used as initial values for simulation studies. The three crystallographic axes on the simulated spectra were well matched with experimental spectra for the two modeled radicals. Thus, we identified the R1 type radical and R4 type radical as paramagnetic species produced in gamma-irradiated 2B4MA.     

Antioxidant and cytotoxic properties of some new dipeptide-indole conjugates

In this study, 10 new indole-dipeptide conjugates were synthesized, and their anticancer activity was determined against on A2780 (ovarian cancer cell line) and MCF-7 (breast cancer cell line) cells. Among compounds, 5 and 10 showed better activity against A2780 cell lines than the standard drug docatexel at 0.1 and 1 μM concentrations, while only compound 5 showed better activity than docatexel, the MCF-7 cell line at 0.1 and 1 μM concentrations. The antioxidant potencies of the compounds were low in both the DPPH and iron reducing power methods tested when compared to standard antioxidants used in this work.