How Do Aromatic Nitro Compounds React with Nucleophiles? Theoretical Description Using Aromaticity, Nucleophilicity and Electrophilicity Indices

In this study, we present a complete description of the addition of a model nucleophile to the nitroaromatic ring in positions occupied either by hydrogen (the first step of the SNAr-H reaction) or a leaving group (SNAr-X reaction) using theoretical parameters including aromaticity (HOMA), electrophilicity and nucleophilicity indices. It was shown both experimentally and by our calculations, including kinetic isotope effect modeling, that the addition of a nucleophile to the electron-deficient aromatic ring is the rate limiting step of both SNAr-X and SNAr-H reactions when the fast transformation of σH-adduct into the products is possible due to the specific reaction conditions, so this is the most important step of the entire reaction. The results described in this paper are helpful for better understanding of the subtle factors controlling the reaction direction and rate.

Sensitivity of Neuromechanical Predictions to Choice of Glenohumeral Stability Modeling Approach

Most upper-extremity musculoskeletal models represent the glenohumeral joint with an inherently stable ball-and-socket, but the physiological joint requires active muscle coordination for stability. The authors evaluated sensitivity of common predicted outcomes (instability, net glenohumeral reaction force, and rotator cuff activations) to different implementations of active stabilizing mechanisms (constraining net joint reaction direction and incorporating normalized surface electromyography [EMG]). Both EMG and reaction force constraints successfully reduced joint instability. For flexion, incorporating any normalized surface EMG data reduced predicted instability by 54.8%, whereas incorporating any force constraint reduced predicted instability by 43.1%. Other outcomes were sensitive to EMG constraints, but not to force constraints. For flexion, incorporating normalized surface EMG data increased predicted magnitudes of joint reaction force and rotator cuff activations by 28.7% and 88.4%, respectively. Force constraints had no influence on these predicted outcomes for all tasks evaluated. More restrictive EMG constraints also tended to overconstrain the model, making it challenging to accurately track input kinematics. Therefore, force constraints may be a more robust choice when representing stability.

DFT study of triplet and singlet elementary acts of acyclic and cyclic alkanes oxidation initiated by primary interaction with 3O2

The primary oxidation stages of 3O2 model acyclic and cyclic alkanes and their subsequent triplet and singlet elementary events were studied for the first time by the DFT method with the density functional B3LYP and basis set 6-311++g(df,p). According to quantum chemical DFT calculations the C–H radical cleavage of the bonds of acyclic and cyclic alkanes upon interaction with 3O2 is almost completely thermodynamically shifted toward the initial state of the reaction system. This energy of primary oxidizing events explains the extremely low reactivity of saturated alkanes in comparison with asphaltene structural fragments under the conditions of SCF technology for the extraction of heavy oils and asphaltenes by a propane-butane mixture. It has been demonstrated that for all elementary acts of primary alkane oxidation the product of the direct reaction direction is not a free pair of radicals but a triplet hydrogen complex with a pronounced hydrogen bond between the hydroperoxyl radical and the radical form of the corresponding hydrocarbon. A new, previously not taken into account very exothermic (H = -29.25 – -30.77 kcal/mol) reaction direction is described which corresponds to triplet recombination of alkyl radicals and a hydroperoxyl radical in its oxygen-concentrated part. The products of this recombination are triplet forms of alkane hydroperoxides in which there is a fairly loosened triplet O---O bond with a length of 2.20-2.23 Å, which is ~0.72-0.77 Å more than bond length in the singlet state.

Comparison of the performance of entrapped and covalently immobilized lipase in the synthesis of pear flavor

Introduction:Although aroma esters are produced mostly by a chemical method that requires the use of aggressive chemical catalysts, enzymatic esterification has been very favored during previous two decades. The main aim of this study was to investigate the commercially important pear flavor, hexyl acetate (HAc), by the catalysis of immobilized lipase samples and to optimize the immobilization and operational conditions in detail.Methods:Lipases fromResults:Among the several organic media, the highest esterification activites were observed in heptane. HAc yield decreased when substrate concentrations were higher than 50 or 75 mM. Yield increased with increase in reaction time up to the 5Discussion and conclusions:As well as synthesis conditions, immobilization parameters also affected HAc productivity. The amount of water in the microenvironment of lipase is so important not only for gaining its active conformation but only for the reaction direction.

A Simplified Method to Assess the Risk of Geotechnical Engineering under Hydro-Chemical Corrosion

Rock mass are subject to continuous changes induced by physical and chemical processes of natural and anthropic origin. Such changes affect their mechanical properties. To quantitatively evaluate the hydro-chemical corrosion, the theories of chemical thermodynamic and chemical kinetics are introduced. An index was proposed, which provides a criterion to judge whether the corrosion would be happened and indicated the reaction direction. Then based on theoretical and testing results, a hydro-chemical damage index was proposed. And a series of damage degrees of sandstone under different circumstances, which consider the variations of pH values, temperatures, ions species and ions concentrations, were calculated by chemical kinetics method. Based on the results, the sensitivity of influencing factors was discussed. According to the calculation and the theory of poromechanics or testing results, the mechanical properties of geotechnical materials under hydro-chemical corrosion process can be predicted, so can assess the risk of geotechnical engineering long-term stability.