Nonequilibrium synthesis

Dai HX, Choe WS, Thai CK, Saiikaya M, Traxler BA, Baneyx F, Schwartz DT (2005) Nonequilibrium synthesis and assembly of hybrid inorganic-protein nanostructures using an engineered DNA binding protein. J Am Chem Soc 127 15637-15643... 

Makki, R., Steinbeck, O. Nonequilibrium synthesis of silica-supported magnetite tubes and mechanical control of their magnetic properties. J. Ame. Chem. Soc. 134, 15519 (2012)... 

Three nonequilibrium reactions catalyzed by hexoki-nase, phosphofructokinase, and pyruvate kinase prevent simple reversal of glycolysis for glucose synthesis (Chapter 17). They are circumvented as follows ... 

Malate is not the only form in which C4 compounds are exported from mitochondria. Much oxaloacetate is combined with acetyl-CoA to form citrate the latter leaves the mitochondria and is cleaved by the ATP-dependent citrate-cleaving enzymes (Eq. 13-39). This, in effect, exports both acetyl-CoA (needed for lipid synthesis) and oxaloacetate which is reduced to malate within the cytoplasm. Alternatively, oxaloacetate may be transaminated to aspartate. The aspartate, after leaving the mitochondria, may be converted in another transamination reaction back to oxaloacetate. All of these are part of the nonequilibrium process by which C4 compounds diffuse out of the mitochondria before completing the reaction sequence of Eq. 17-46 and entering into other metabolic processes. Note that the reaction of Eq. 17-46 leads to the export of reducing equivalents from mitochondria, the opposite of the process catalyzed by the malate-aspartate shuttle which is discussed in Chapter 18 (Fig. 18-18). The two processes are presumably active under different conditions. 

A quantitative description of oxidative phosphorylation within the cellular environment can be obtained on the basis of nonequilibrium thermodynamics. For this we consider the simple and purely phenomenological scheme depicted in Fig. 1. The input potential X0 applied to the converter is the redox potential of the respiratory substrates produced in intermediary metabolism. The input flow J0 conjugate to the input force X0 is the net rate of oxygen consumption. The input potential is converted into the output potential Xp which is the phosphate potential Xp = -[AG hoS -I- RT ln(ATP/ADP P,)]. The output flow Jp conjugate to the output force Xp is the net rate of ATP synthesis. The ATP produced by the converter is used to drive the ATP-utilizing reactions in the cell which are summarized by the load conductance L,. Since the net flows of ATP are large in comparison to the total adenine nucleotide pool to be turned over in the cell, the flow Jp is essentially conservative. 

Novel applications have been developed from the combination of microreactor technology and nonequilibrium microplasma chemistry. Here we discuss a selection from the recent literature on this topic to illustrate several main trends. We will focus on microplasmas in confined microchannels for the purpose of chemical synthesis and environmental applications. 

Entropy is closely related to heat (enthalpy) and energy. If all the ATP available from catabolic processes were used for anabolism (chemical synthesis), up to ten times more cellular material could be produced. First investigations of this large outflow of entropy from growing cells have been made by Bormann [40] however, classical thermodynamics are hardly applicable to complex, nonequilibrium metabolic systems and must be extended [458]. 

Abstract. Structural and adsorption characteristics of various adsorbents such as fumed silicas, silica gels, activated carbons and carbon/silicas were analyzed. The adsorption of a variety of compounds reveals the effects of adsorbent grain size, specific surface area, pore volume, pore size distribution, surface chemistry, conditions of adsorbent synthesis and pre-treatment. Both dynamic (nonequilibrium) and static (equilibrium) adsorption conditions are addressed. 

Laboratory production of dust analogs is a highly specialized field that attempts to reproduce a subset of the basic properties of the solids that we expect to exist in a particular astrophysical environment. The synthesis of dust in the outflows of evolved stars, however, is a much more complex process that occurs under nonequilibrium, continuously changing conditions and with the participation of many more chemical elements than can be accommodated by any practical experimental... 

This book is a synopsis of lectures on thermodynamics of nonequilib rium processes and from a course on thermodynamics of operating cata lysts, both from Novosibirsk State University. The content of this book mostly reflects the author s particular scientific interests. Therefore, the author apologizes to those who expected to find information on irrevers ible processes Hke diffusion in synthesis materials. It is hoped that the author s approach to teaching nonequilibrium thermodynamics will be adopted by others. 

NONEQUILIBRIUM NONDISSIPATIVE THERMODYNAMICS AND ITS APPLICATION TO MODERN INORGANIC SYNTHESIS... 

Wang J.-T, Nonequilibrium nondissipative thermodynamics with application to low-pressure diamond synthesis (Springer, Heidelberg, 2002) 254 pages. 

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