Thermodynamics of lipophilic drug binding to intestinal fatty acid binding protein and permeation across membranes

Intestinal fatty acid binding protein (I-FABP) is present at high levels in the absorptive cells of the intestine (enterocytes), where it plays a role in the intracellular solubilization of fatty acids (FA). However, I-FABP has also been shown to bind to a range of non-FA ligands, including some lipophilic drug molecules. Thus, in addition to its central role in FA trafficking, I-FABP potentially serves as an important intracellular carrier of lipophilic drugs. In this study we provide a detailed thermodynamic analysis of the binding and stability properties of I-FABP in complex with a series of fibrate and fenamate drugs to provide an insight into the forces driving drug binding to I-FABP. Drug binding and selectivity for I-FABP are driven by the interplay of protein−ligand interactions and solvent processes. The Gibbs free energies (ΔG°) determined from dissociation constants at 25 °C ranged from −6.2 to −10 kcal/mol. The reaction energetics indicate that drug binding to I-FABP is an enthalpy−entropy driven process. The relationship between I-FABP stability and drug binding affinity was examined by pulse proteolysis. There is a strong coupling between drug binding and I-FABP stability. The effect of an I-FABP protein sink on the kinetics and thermodynamics of tolfenamic acid permeation across an artificial phospholipid membrane were investigated. I-FABP significantly decreased the energy barrier for desorption of tolfenamic acid from the membrane into the acceptor compartment. Taken together, these data suggest that the formation of stable drug−I-FABP complexes is thermodynamically viable under conditions simulating the reactant concentrations likely observed in vivo and maybe a significant biochemical process that serves as a driving force for passive intestinal absorption of lipophilic drugs.

A study on the thermodynamics of in situ MgAl2O4/Al MMC formation using amorphous silica sources

MgAl₂O₄ (spinel) is considered as a commercially important ceramic reinforcement in MMC fabrication because of the possible tailorable properties imparted with Al for many applications. Generally, any oxygen source, i.e., the dissolved oxygen, or pure oxygen atmosphere or atmospheric oxygen is sufficient for the formation of MgAl₂O₄ in Al–Mg alloy. Among all the reactive oxygen sources, the reactivity of SiO₂ with Al alloy is found to be higher. Amorphous silica is highly reactive in nature compared to crystalline silica. The present study has examined the thermodynamics of MgAl₂O₄ formation in Al–Mg alloy by amorphous silica sources with the aid of differential thermal analyzer (DTA) and the simulated experiments. The dissolution of Si and the formation of MgAl₂O₄ are detected as the endothermic peak and the immediate exothermic peak respectively in DTA curves and the presence of MgAl₂O₄ is confirmed by the XRD of the simulated sample. The MgO formed due to the oxidation of Mg in Al–Mg alloy has been found to influence the MgAl₂O₄ formation.

Thermodynamics and kinetics of the formation of Al2 O3/ MgAl2O4/MgO in Al-Silica metal matrix composite

The formation of Al₂O₃, MgAl₂O₄, and MgO has been widely studied in different Al base metal matrix composites, but the studies on thermodynamic aspects of the Al₂O₃/ MgAl₂O₄/MgO phase equilibria have been limited to few systems such as Al/Al₂O₃ and Al/SiC. The present study analyzes the Al₂O₃/MgAl₂O₄ and MgAl₂O₄/MgO equilibria with respect to the temperature and the Mg content in Al/SiO2 system using an extended Miedema model. There is a linear and parabolic variation in Mg with respect to the temperature for MgAl₂O₄/MgO and Al₂O₃/MgAl₂O₄ equilibria, respectively, and the influence of Si and Cu in the two equilibria is not appreciable. The experimental verification has been limited to MgAl₂O₄/MgO equilibria due to the high Mg content (≥0.5 wt pct) required for composite processing. The study has been carried out on two varieties of Al/SiO₂ composites, i.e., Al/Silica gel and Al/Micro silica processed by liquid metallurgy route (stir casting route). MgO is found to be more stable compared to MgAl₂O₄ at Mg levels ≥5 and 1 wt pct in Al/Silica gel and Al/Micro silica composites, respectively, at 1073 K. MgO is also found to be more stable at lower Mg content (3 wt pct) in Al/Silica gel composite with decreasing particle size of silica gel from 180 micron to submicron and nanolevels. The MgO to MgAl₂O₄ transformation has taken place through a series of transition phases influenced by the different thermodynamic and kinetic parameters such as holding temperature, Mg concentration in the alloy, holding time, and silica particle size.

Thermodynamics approach to the hydrogen diffusion and phase transformation in titanium particles

The hydrogen diffusion and phase transformation in a titanium particle were studied based on thermodynamic calculation. The mechanisms of hydrogen diffusion in different phases (alpha-Ti, beta-Ti and TiHx) were analyzed. A mobility database was developed for titanium– hydrogen system based on the experimental works on hydrogen diffusion coefficient reported in literature and the fundamental of diffusion. To implement the calculation, a commercial software package for the simulation of diffusion-controlled phase transformation was used. The hydrogen diffusion process, hydrogen distribution, phase transformation and phase growth rate during hydrogenization of a titanium particle at temperatures of 560 K, 800K and 1000K were discussed. The thermodynamics and kinetics analysis provided quantitative insight into the diffusion process and improved the understanding of diffusion mechanism and phase transformation.

Evaluation of cassava peel waste as lowcost biosorbent for Ni-sorption : equilibrium, kinetics, thermodynamics and mechanism

The feasibility of cassava peel waste for Ni-sorption is evaluated in this work. The biosorbents are characterized by Boehm titration, Fourier transform-infra red (FTIR) spectroscopy, Nitrogen sorption, scanning electron microscopy-energy dispersive X-ray (SEM-EDX) analysis (e.g. elemental mapping) and X-ray photoelectron spectroscopy (XPS). Adsorption experiments are performed in batch mode at 30 °C (303.15 K), 45 °C (318.15 K) and 60 °C (333.15 K). The performance of several temperature dependence forms of isotherm models e.g. Langmuir, Freundlich, Sips and Toth to represent the adsorption equilibrium data is evaluated and contrasted. Sips model demonstrates the best fitting with the maximum uptake capacity for Ni(II) ions of 57 mg/g (0.971 mmol/g) at pH 4.5. For kinetic data correlation, pseudo-second order model shows the best representation. The chemisorption mechanism and thermodynamics aspect are also discussed.

Engineering of small-molecule gels based on the thermodynamics and kinetics of fiber formation

In this chapter, we will give an overview of our work on manipulating the micro/nano structure and macroscopic properties of SMGs. Firstly, it will cover the analysis of the thermodynamics of fiber formation in SMGs and the classification and characterization of the topological and micro/nano structures of fiber networks, followed by the analysis of the formation kinetics of these networks. The criteria of engineering of the SMGs will be summarized according to the latest understanding of the formation mechanisms of fiber networks. On the basis of this understanding, approaches that have been developed to engineer the micro/nanometer structures and macroscopic properties of typical SMGs will be presented.

A solar collector with the absorber divided by rectangular slots

A new solar absorber structure has been proposed and studied in this paper. The metal tubes running perpendicular to a set of parallel rectangular metal fins make the solar absorber with rectangular slots. Studies on the collector were theoretically carried out in the aspects of heat transfer, thermodynamics and . hydrodynamics. The calculating methods for calculating fin efficiency F and efficiency factors of the collector F' were obtained. The results showed that the new solar collector would have the higher efficiency and better performance at higher fluid temperature than that of the traditional flat-plate collectors. A collector prototype with the new structure was built and tested. The testing results agree with our theoretical results.

Growth and structure of prismatic boron nitride nanorods

Prismatic boron nitride nanorods have been grown on single crystal silicon substrates by mechanical ball-milling followed by annealing at 1300 °C. Growth takes place by rapid surface diffusion of BN molecules, and follows heterogeneous nucleation at catalytic particles of an Fe/Si alloy. Lattice imaging transmission electron microscopy studies reveal a central axial row of rather small truncated pyramidal nanovoids on each nanorod, surrounded by three basal planar BN domains which, with successive deposition of epitaxial layers adapt to the void geometry by crystallographic faceting. The bulk strain in the nanorods is taken up by the presence of what appear to be simple nanostacking faults in the external, near-surface domains which, like the nanovoids are regularly repetitive along the nanorod length. Growth terminates with a clear cuneiform tip for each nanorod. Lateral nanorod dimensions are essentially determined by the size of the catalytic particle, which remains as a foundation essentially responsible for base growth. Growth, structure, and dominating facets are shown to be consistent with a system which seeks lowest bulk and surface energies according to the well-known thermodynamics of the capillarity of solids.

Thermodynamic and kinetic modelling hydrogenation of titanium particles and sheets

Use of hydrogen as a temporary alloying element in titanium alloys is an attractive approach to improve the mechanical properties of the materials, enhance processability and thereby reduce manufacturing costs. In this paper, the hydrogen diffusion process and the phase transformation both between titanium particles and in titanium sheets were computationally simulated to analyze the mechanism of hydrogen diffusion in different phases (α-Ti, β-Ti and TiHx). With the simulation based on the thermodynamics and kinetics, quantitative behaviors of the hydrogen diffusion and the phase transformation were analyzed. The simulation results provide an insight into the diffusion process and improve the fundamental understanding of the mechanism of diffusion and phase transformation.

Available energy

A proposed new statement of the second law of thermodynamics - the transformation of energy to work is always inefficient with respect to available energy - is conceptually and pedagogically simpler than historical entropy-based statements. It has assisted in the discovery of a new general characterisation of steady (energy dissipative) states.

Microstructural development in Al/MgAl2O4 in situ metal matrix composite using value-added silica sources

Al/MgAl2O4 in situ metal matrix composites have been synthesized using value-added silica sources (microsilica and rice husk ash) containing ~97% SiO2 in Al-5 wt.% Mg alloy. The thermodynamics and kinetics of MgAl2O4 formation are discussed in detail. The MgO and MgAl2O4 phases were found to dominate in microsilica (MS) and rice husk ash (RHA) value-added composites, respectively, during the initial stage of holding the composites at 750 °C. A transition phase between MgO and MgAl2O4 was detected by the scanning electron microscopy and energy-dispersive spectroscopy (SEM–EDS) analysis of the particles extracted from the composite using 25% NaOH solution. This confirms that MgO is gradually transformed to MgAl2O4 by the reaction 3SiO2(s)+2MgO(s)+4Al(l)→2MgAl2O4(s)+3Si(l). The stoichiometry of MgAl2O4, n, computed by a new methodology is between 0.79 and 1.18. The reaction between the silica sources and the molten metal stopped after 55% of the silica source was consumed. A gradual increase in mean MgAl2O4 crystallite size, D, from 24 to 36 nm was observed in the samples held for 10 h.

Synthesis of an Al/MgAl2O4 in situ metal matrix composite from silica gel

An aluminum/MgAl2O4 in situ metal matrix composite has been synthesized using silica gel containing B98% SiO2 in an Al–5Mg alloy. The thermodynamics and kinetics of MgAl2O4 formation have been discussed in detail. A transition phase of composition between MgO and MgAl2O4 has been detected in the SEM-EDS analysis of the particles extracted from the composite by a 25% NaOH solution. This confirms the gradual transformation of MgO to MgAl2O4 by the reaction 3SiO2(s)12MgO(s)14Al(l)-2MgAl2O4(s)13Si(l). The stoichiometry, n, of MgAl2O4 has been found to sustain close to 1 and the crystallite growth of MgAl2O4 has been stopped at DB30 nm in the composites held at 7501C up to 10 h.

A study on the formation of MgAl2O4 and MgO crystals in Al-Mg/quartz composite by differential thermal analysis

The present study has examined the thermodynamics of MgAl₂O₄ and MgO formations in Al–Mg alloy/quartz (>99% crystalline silica) through differential thermal analysis (DTA). The formation of MgAl₂O₄ and MgO is detected as exothermic peaks in the heat flow curve and the reaction is confirmed by the Si dissolution peaks observed during the reheating of samples and SEM analysis of the reacted sample. The presence of MgAl₂O₄ and MgO is confirmed in the XRD analysis of the reacted sample. The study has enabled the production of nano sized MgAl₂O₄ and MgO crystals at the interface of Al–Mg alloy and quartz. The reaction between them is found to be influenced by the oxidation of Mg, which is reduced by increasing heating rates.

Exergy applied to lunar base design

This paper explores design considerations for energy efficiency in lunar habitats. It considers several previous lunar energy studies in regards to energy types and stages of energy requirements. If we are to obtain true sustainability in energy processes, we will need to design according to the principles “exergy”, considering both the first and the second laws of thermodynamics in a holistic and thorough evaluation of energy capture, transformation, and use. Such an evaluation will ascertain the source of energy, its processing and energy potential stages, as well as the task required. Traditional designs of facility thermal systems are frequently extremely wasteful: they dramatically increase both first costs and operating costs because they treat heating and cooling systems as separate entities, instead of an integrated energy system. Energy processes, the state of energy required to do a particular task, the embodied energy to complete or manufacture an object, and the wasted energy released are all important to conservation and obtaining an efficient and effective use (quality) of energy. If the regulation of energy processes is a concern in terrestrial habitation, it should be even more so for extra-terrestrial habitation where there is little margin for waste of any sort.

Physical principles of membrane organization

Membranes are the most common cellular structures in both plants and animals. They are now recognized as being involved in almost all aspects of cellular activity ranging from motility and food entrapment in simple unicellular organisms, to energy transduction, immunorecognition, nerve conduction and biosynthesis in plants and higher organisms. This functional diversity is reflected in the wide variety of lipids and particularly of proteins that compose different membranes. An understanding of the physical principles that govern the molecular organization of membranes is essential for an understanding of their physiological roles since structure and function are much more interdependent in membranes than in, say, simple chemical reactions in solution. We must recognize, however, that the word ‘understanding’ means different things in different disciplines, and nowhere is this more apparent than in this multidisciplinary area where biology, chemistry and physics meet.