Aromatic B3 Ring Stabilized Group 2 Dimer, B3-Y-Y-B3 (Y = Be, Mg, Ca)

Quantum chemical calculations have been performed on B3 ring stabilized Y-Y interaction (Y = Be, Mg, Ca) to understand the possibility of binuclear sandwich type complex formation. Calculations indicate single reference character of the studied systems. The complexes have been found to be stable towards dissociation into different fragments. Thermodynamic consideration also indicates the favourability of their formation. Increase in aromaticity of the parent B3 ring upon complexation is observed which is expected to provide extra stability to the complexes.

Hardness–Deformation Energy Relationship in Metals and Alloys: A Comparative Evaluation Based on Nanoindentation Testing and Thermodynamic Consideration

Nanoindentation testing using a Berkovich indenter was conducted to explore the relationships among indentation hardness (H), elastic work energy (We), plastic work energy (Wp), and total energy (Wt = We + Wp) for deformation among a wide range of pure metal and alloy samples with different hardness, including iron, steel, austenitic stainless steel (H ≈ 2600–9000 MPa), high purity copper, single-crystal tungsten, and 55Ni–45Ti (mass%) alloy. Similar to previous studies, We/Wt and Wp/Wt showed positive and negative linear relationships with elastic strain resistance (H/Er), respectively, where Er is the reduced Young’s modulus obtained by using the nanoindentation. It is typically considered that Wp has no relationship with We; however, we found that Wp/We correlated well with H/Er for all the studied materials. With increasing H/Er, the curve converged toward Wp/We = 1, because the Gibbs free energy should not become negative when indents remain after the indentation. Moreover, H/Er must be less than or equal to 0.08. Thermodynamic analyses emphasized the physical meaning of hardness obtained by nanoindentation; that is, when Er is identical, harder materials show smaller values of Wp/We than those of softer ones during nanoindentation under the same applied load. This fundamental knowledge will be useful for identifying and developing metallic materials with an adequate balance of elastic and plastic energies depending on the application (such as construction or medical equipment).

A Green’s function perspective on the nonequilibrium thermodynamics of open quantum systems strongly coupled to baths

We give a nonequilibrium Green’s function (NEGF) perspective on thermodynamics formulations for open quantum systems that are strongly coupled to baths. A scattering approach implying thermodynamic consideration of a supersystem (system plus baths) that is weakly coupled to external superbaths is compared with the consideration of thermodynamics of a system that is strongly coupled to its baths. We analyze both approaches from the NEGF perspective and argue that the latter yields a possibility of thermodynamic formulation consistent with a dynamical (quantum transport) description.

Racemization in Post-Translational Modifications Relevance to Protein Aging, Aggregation and Neurodegeneration: Tip of the Iceberg

Homochirality of DNA and prevalent chirality of free and protein-bound amino acids in a living organism represents the challenge for modern biochemistry and neuroscience. The idea of an association between age-related disease, neurodegeneration, and racemization originated from the studies of fossils and cataract disease. Under the pressure of new results, this concept has a broader significance linking protein folding, aggregation, and disfunction to an organism’s cognitive and behavioral functions. The integrity of cognitive function is provided by a delicate balance between the evolutionarily imposed molecular homo-chirality and the epigenetic/developmental impact of spontaneous and enzymatic racemization. The chirality of amino acids is the crucial player in the modulation the structure and function of proteins, lipids, and DNA. The collapse of homochirality by racemization is the result of the conformational phase transition. The racemization of protein-bound amino acids (spontaneous and enzymatic) occurs through thermal activation over the energy barrier or by the tunnel transfer effect under the energy barrier. The phase transition is achieved through the intermediate state, where the chirality of alpha carbon vanished. From a thermodynamic consideration, the system in the homo-chiral (single enantiomeric) state is characterized by a decreased level of entropy. The oscillating protein chirality is suggesting its distinct significance in the neurotransmission and flow of perceptual information, adaptive associative learning, and cognitive laterality. The common pathological hallmarks of neurodegenerative disorders include protein misfolding, aging, and the deposition of protease-resistant protein aggregates. Each of the landmarks is influenced by racemization. The brain region, cell type, and age-dependent racemization critically influence the functions of many intracellular, membrane-bound, and extracellular proteins including amyloid precursor protein (APP), TAU, PrP, Huntingtin, α-synuclein, myelin basic protein (MBP), and collagen. The amyloid cascade hypothesis in Alzheimer’s disease (AD) coexists with the failure of amyloid beta (Aβ) targeting drug therapy. According to our view, racemization should be considered as a critical factor of protein conformation with the potential for inducing order, disorder, misfolding, aggregation, toxicity, and malfunctions.

COMPARATIVE ANALYSIS OF ADSORPTION AND CORROSION INHIBITIVE PROPERTIES OF ETHANOL EXTRACT OF DIALIUM GUINEENSE LEAVES FOR MILD STEEL IN 0.5M HCL

In this study, the adsorption and corrosion inhibitive properties of ethanol extract of Dialium guineense leaves for mild steel in 0.5M HCl was studied using gravimetric method. The results obtained showed that the ethanol extract of Dialium guineense leave is a good adsorption inhibitor of Mild Steel in 0.5M HCl. The inhibition efficiency was found to increase with increase in the concentration of ethanol extract of Dialium guineense leave but decreased as the temperature increases. The inhibition efficiency increases up to a maximum of 92%. The kinetic study was found to follow pseudo first order reaction with high correlation. Thermodynamic consideration reveals that adsorption of ethanol extract of Dialium guineense leaves on mild steel surface is exothermic, spontaneous and fitted the Langmuir adsorption isotherm. The value of activation energy and Gibb’s free energy obtained were within the range of limits expected for the mechanism of physical adsorption. Adeniji, E. S. | Department of Chemistry, Ahmadu Bello University (ABU) Zaria, Kaduna State, Nigeria

Hydrate Production Philosophy and Thermodynamic Calculations

The amount of energy in the form of natural gas hydrates is huge and likely substantially more than twice the amount of worldwide conventional fossil fuel. Various ways to produce these hydrates have been proposed over the latest five decades. Most of these hydrate production methods have been based on evaluation of hydrate stability limits rather than thermodynamic consideration and calculations. Typical examples are pressure reduction and thermal stimulation. In this work we discuss some of these proposed methods and use residual thermodynamics for all phases, including the hydrate phase, to evaluate free energy changes related to the changes in independent thermodynamic variables. Pressures, temperatures and composition of all relevant phases which participate in hydrate phase transitions are independent thermodynamic variables. Chemical potential and free energies are thermodynamic responses that determine whether the desired phase transitions are feasible or not. The associated heat needed is related to the first law of thermodynamics and enthalpies. It is argued that the pressure reduction method may not be feasible since the possible thermal gradients from the surroundings are basically low temperature heat that is unable to break water hydrogen bonds in the hydrate–water interface efficiently. Injecting carbon dioxide, on the other hand, leads to formation of new hydrate which generates excess heat compared to the enthalpy needed to dissociate the in situ CH4 hydrate. But the rapid formation of new CO2 hydrate that can block the pores, and also the low permeability of pure CO2 in aquifers, are motivations for adding N2. Optimum mole fractions of N2 based on thermodynamic considerations are discussed. On average, less than 30 mole% N2 can be efficient and feasible. Thermal stimulation using steam or hot water is not economically feasible. Adding massive amounts of methanol or other thermodynamic inhibitors is also technically efficient but far from economically feasible.

Corrosion and Kinetic Study of Eucalyptus camaldulensis Seeds Extract Percolated with Methanol on Aluminium Coupons in HCl

This research discusses a detail optimization of Eucalyptus camaldulensis seeds extract as corrosion inhibitor for aluminum coupons in HCl using weight loss measurement and kinetic study. The result shows that the maximum inhibitor efficiency was obtained at a concentration of 2.0 (%W/V). However the highest inhibitor efficiency of 85% was obtained at 50ºC and the least inhibitor efficiency of 29% was obtained at 30ºC. Thermodynamic consideration revealed that adsorption of inhibitor of aluminum surface was exothermic and consistent with chemical adsorption mechanism.

Thawing and freezing quintessence models: a thermodynamic consideration

Thawing and freezing quintessence models are compared thermodynamically. Both of them are found to disobey the generalized second law of thermodynamics. However, for freezing models, there is still a scope as this breakdown occurs in the past, deep inside the radiation dominated era, when a standard scalar field model with a pressureless matter is not a correct description of the matter content. The thawing model has a pathological breakdown in terms of thermodynamics in a finite future.

Simulation of Batch Slow Pyrolysis of Biomass Materials Using the Process-Flow-Diagram COCO Simulator

The commercial COCO simulation program was used to mimic the experimental slow pyrolysis process of five different biomasses based on thermodynamic consideration. The program generated the optimum set of reaction kinetic parameters and reaction stoichiometric numbers that best described the experimental yields of solid, liquid and gas products. It was found that the simulation scheme could predict the product yields over the temperature range from 300 to 800 °C with reasonable accuracy of less than 10% average error. An attempt was made to generalize the biomass pyrolysis behavior by dividing the five biomasses into two groups based on the single-peak and two-peak characteristics of the DTG (derivative thermogravimetry) curves. It was found that this approximate approach was able to predict the product yields reasonably well. The proposed simulation method was extended to the analysis of slow pyrolysis results derived from previous investigations. The results obtained showed that the prediction errors of product yields were relatively large, being 12.3%, 10.6%, and 27.5% for the solid, liquid, and gas products, respectively, possibly caused by differing pyrolysis conditions from those used in the simulation. The prediction of gas product compositions by the simulation program was reasonably satisfactory, but was less accurate for predicting the compositions of liquid products analyzed in forms of hydrocarbons, aromatics and oxygenated fractions. In addition, information on the kinetics of thermal decomposition of biomass in terms of the variation of fractional conversion with time was also derived as a function of temperature and biomass type.