Structure, thermal behavior, and IR investigation of bis(3-amino-1,2,4-triazolium)monohydrogen monophosphate

Chemical preparation, calorimetric studies, crystal structure, and IR spectrometric investigation of (C₂H₅N₄)₂HPO₄, denoted ATZP, are described. The compound crystallizes in the monoclinic system with C2/c space group. Its unit cell dimensions are a = 13.589(2) Å b = 11.105(2) Å c = 15.734(3) Å = 104.68(2)°, V = 2296.8(7) ų, and Z = 8. The structure of the title compound consists of a three dimensional network of H-bonds connecting all its components. The IR spectrum of ATZP is reported and discussed on the basis of group theoretical analysis.     

Alkylation of natural endoperoxide G3-factor. Synthesis and antimalarial activity studies

Alkylation of the peroxyhemiketal function is described and all synthesised endoperoxides show good antimalarial activity. New rearrangement reactions in the presence of CsCO3, and preliminary results on Fe(II) chemical reduction of the O-O bond are presented.     

Fe(II)-induced reduction of labelled endoperoxides. NMR degradation studies on G3 factor and its methyl ether

The behavior of G3 factor and of its methylated or fluorinated analogues G3Me and G3F, was studied under Fe(II) conditions. Degradation products were isolated and characterized in each case. The use of labelled compounds allowed us to propose mechanisms in which a tertiary radical is involved. This radical rearranges by 5-exo-trig cyclization, or disproportionates in the case of G3Me. A correlation between antiplasmodial activity and stability of this radical is proposed.     

Electrochemical reduction of G3-factor endoperoxide and its methyl ether: evidence for a competition between concerted and stepwise dissociative electron transfer

The reduction of the bicyclic G-factor endoperoxides G3 and G3Me was studied in N,N-dimethylformamide using cyclic voltammetry and convolution analysis. Electron transfer leads to irreversible cleavage of the O--O bond. Detailed analysis of the voltammetry curves reveals a non-linear dependence on the transfer coefficient indicating a mechanistic transition from a stepwise mechanism to one with more concerted character with increasing potential. By using quantum calculations to estimate the O--O bond dissociation energies, the experimental data was used to evaluate the standard reduction potentials and other pertinent thermochemical information.     

Thermal performance of an integrated collector storage solar water heater (ICSSWH) with a storage tank equipped with radial fins of rectangular profile

The thermal behavior of an integrated collector storage solar water heater (ICSSWH) is numerically studied using the package Fluent 6.3. Based on the good agreement between the numerical results and the experimental data of Chaouachi and Gabsi (Renew Energy Revue 9(2):75–82, 2006), an attempt to improve this solar system operating was made by equipping the storage tank with radial fins of rectangular profile. A second 3D CFD model was developed and a series of numerical simulations were conducted for various SWH designs which differ in the depth of this extended surface for heat exchange. As the modified surface presents a higher characteristic length for convective heat transfer from the storage tank to the water, the fins equipped storage tank based SWH is determined to have a higher water temperature and a reduced thermal losses coefficient during the day-time period. Regarding the night operating of this water heater, the results suggest that the modified system presents higher thermal losses.     

Effect of the storage tank thermal insulation on the thermal performance of an integrated collector storage solar water heater (ICSSWH)

The thermal behavior of an integrated collector storage solar water heater (ICSSWH) is numerically studied using CFD simulations. Based on the good agreement between the numerical results and the experimental data from literature, we propose a geometrical change allowing limiting the main disadvantage of this solar system which is its high night losses due to the non-insulated storage tank surface. A second 3D CFD model of an ICSSWH in which the storage tank is partially insulated is developed and three values of this tank thermal insulated fraction are studied. Numerical results show that the partially insulated tank based ICSSWH presents lower thermal losses during the night and this night thermal losses coefficient is reduced from 14.6 to 11.64 W K^?1 for the tank thermal insulation fraction τ = 1/4. Similarly, the modified system presents the advantage of its lower thermal losses even during the day. Regarding the thermal production, it is seen that the modified system presents higher water temperature at night and that for all the tank thermal insulation fractions. Concerning the operation of this modified system during the day, the water temperature is lower during the day and that up to 16 h but the water temperature which achieves 324 K for the storage tank thermal insulation fraction τ = 1/8 still sufficiently high to satisfy a family hot water needs.     

Evidences of Electronic Effects in the Vibrational Spectra of Some Rhodium(II) Carboxylate Complexes

Abstract

Abstract - A series of dirhodium tetracarboxylate complexes, containing triphenylphosphine as axial ligand was investigated by electronic and Raman spectroscopy, aiming to detect the influence of electronic effects of the carboxylate substituents on the v₁[v_(RhRh)] and v₂[v_(RhO)] Modes. When pairs of complexes with similar molecular weights are compared, as in the case of the cyclopentanecarboxylate and trifluoroacetate complexes, the striking difference in the inductive character of the two species results in substantial shifts of the v₁ and v₂ modes as a consequence of variations in the corresponding force constants rather than a simple mass effect as previously observed for non-substituted rhodium-carboxylates.     

Determination of benzoylurea insecticides in food by pressurized liquid extraction and LC‐MS

A method based on pressurized liquid extraction and LC‐MS/MS has been developed for determining nine benzoylureas (BUs) in fruit, vegetable, cereals, and animal products. Samples (5 g) were homogenized with diatomaceous earth and extracted in a 22 mL cell with 22 mL of ethyl acetate at 80°C and 1500 psi. After solvent concentration and exchange to methanol, BUs were analyzed by LC‐MS/MS using an IT mass analyzer, which achieved several transitions of precursor ions that increase selectivity providing identification. LOQs were between 0.002 and 0.01 mg/kg, which are equal or lower than maximum residue limits established by the Codex Alimentarius. Excellent linearity was achieved over a range of concentrations from 0.01 to 1 mg/kg with correlation coefficients 0.995–0.999 (n=7). Validation of the total method was performed by analyzing in quintuplicate seven different commodities (milk, eggs, meat, rice, lettuce, avocado, and lemon) at three concentration levels (0.01, 0.1, and 1 mg/kg). The recoveries ranged from 58 to 97% and the RSDs from 5 to 19% depending on the compound and the commodity. The combination of pressurized liquid extraction with LC‐MS/MS provides a sensitive and selective method for the determination of BUs in food.