Theory of surface metabolism

Wachtershauser, G. (1988). Before enzymes and templates theory of surface metabolism. Microbiol. Rev. 52,452-84. 

One of the most interesting is the theory of surface metabolism, an approach that was proposed, in different forms, by John Bernal in 1951, by Graham Cairns-Smith in 1982 and by Gunter Wachters-hauser in 1998. The central idea of this theory is based on solid thermodynamic arguments. The formation of a peptide bond is not favoured in solution because it increases the entropy of the system, but on a surface the same process takes place with a decrease of entropy, and is therefore favoured. And this is true not only for peptide bonding but for many other types of polymerisation. A great number of enzymatic reactions require a collision of three molecules, an event which is highly unlikely in space but much more probable on a surface. 

The RNA world requires a system capable of self-replication as a precondition for the beginnings of life. In contrast, the surface metabolism theory proposed by Wachtershauser postulates that the initial step is metabolism, from which complex replication systems can evolve later. This metabolism would have occurred at the... 

The theory is based on the autotrophic metabolism of low-molecular-weight constituents in an environment of iron sulfide and hot vents. Figure 2.4 gives an illustration of one reaction pathway. It is worthwhile to consider that the metabolism is a surface metabolism, namely with a two-dimensional order, based on negatively charged constituents on a positively charged mineral surface. Actually Wachtershauser sees this as an interesting part of a broader philosophical view (Huber and Wachtershauser, 1997). 

Semiconductors are considered to be catalytic particles that contributed to the development of primitive metabolism. According to Wahtershauser life could have developed on the surface of iron sulphide minerals (eg mackinawite or pyrrhotite [FeS] or pyrite [FeS2]) [8], The chemoautotrophy theory is based on the reaction between iron sulphide and hydrogen sulphide, which acts as a reducing agent, whereas iron sulphide provides adsorption sites for substrates and acts as a catalyst (equation 10.1) ... 

Lipid removal may be a critical factor in plaque formation and the location of lecithin-cholesterol trans-acylase in the arterial wall could play an important role since cholesterol is rapidly exchanged" with the blood while cholesterol ester is not. Kuo in an editorial cites the evidence for the theory that a dlsturbemce in carbohydrate metabolism can be responsible for atherosclerosis and should be included as one of the primary risk factors in coronary heart disease. In this regard, Clements and coworkers have shown the presence in aorta of aldose reductase, an enzyme which they feel provides a mechanism for the alteration of arterial metabolism by hyperglycemia. Another approach to molecular interactions was described by Levy and Day who concluded from their results that the low density lipoproteins are uniquely polycationic at the surface and that these ions react with the internal arterial macromolecular polyanions. 

An attractive hypothesis is the independent evolution in bacteria of their diffusible individualites and the currently recognized secondary metabolic pathways, in parallel with their surface components and their biosynthesis. An indicator for this would be the use of the same gene pool. The theory would include all substances that play a role in the build-up of glycan and other modified surface layers, lipids, murein, (glyco-) proteins (e.g., S-layers), polysaccharides, teichoic... 

The common ancestor of life was probably a chemoautotrophic hyperthermophilic anaerobe. This metabolism first theory assumes that life started with catalytic metal sulfide surface/compartments in a hydro thermal-vent setting in the Hadean... 

Adaptive Enzyme Theory. The aliesterases are largely found in the microsomes of rat liver cells (44). Recently Hart and Fouts (51,52, 67-69) have presented evidence that in vivo administration of chlordan or chemically related DDT stimulates the activity of hepatic microsomal drug-metabolizing enzymes, as evidenced by proliferation of smooth-surfaced endoplasmic reticulum (SER) which was first noted with phenobarbital. Several reviews of hepatic drug metabolism... 

Figure 4.19 Mapping of the electrostatic potential on the electron isodensity surface (red and blue denote negative and positive partial charges, respectively B3LYP/6-31 G //AM1 level of theory) [30] indicates the electrostatic similarity of 4-nitrophenyl and 3,4-difluorophenyl residue (top). Replacement of a nitro group by ortho difluoro substitution in pharmaceuticals results in comparable biological activity but far greater metabolic stability and reduced toxicity (bottom) [61].

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