PubMed Health⌕ Search

PubMed · 16939622

Steady-state kinetic behaviour of functioning-dependent structures.

Abstract

A fundamental problem in biochemistry is that of the nature of the coordination between and within metabolic and signalling pathways. It is conceivable that this coordination might be assured by what we term functioning-dependent structures (FDSs), namely those assemblies of proteins that associate with one another when performing tasks and that disassociate when no longer performing them. To investigate a role in coordination for FDSs, we have studied numerically the steady-state kinetics of a model system of two sequential monomeric enzymes, E(1) and E(2). Our calculations show that such FDSs can display kinetic properties that the individual enzymes cannot. These include the full range of basic input/output characteristics found in electronic circuits such as linearity, invariance, pulsing and switching. Hence, FDSs can generate kinetics that might regulate and coordinate metabolism and signalling. Finally, we suggest that the occurrence of terms representative of the assembly and disassembly of FDSs in the classical expression of the density of entropy production are characteristic of living systems.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Michel Thellier, Guillaume Legent, Patrick Amar, Vic Norris, Camille Ripoll. 2006. Steady-state kinetic behaviour of functioning-dependent structures.. https://doi.org/10.1111/j.1742-4658.2006.05425.x

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related citations

Photosynthetic reaction center mimicry of a "special pair" dimer linked to electron acceptors by a supramolecular approach: self-assembled cofacial zinc porphyrin dimer complexed with fullerene(s).

Biomimetic bacterial photosynthetic reaction center complexes have been constructed using well-defined self-assembled supramolecular approaches. The "special pair" donor, a cofacial porphyrin dimer, was formed via potassium ion induced dimerization of meso-(benzo-[15]crown-5)porphyrinatozinc. The dimer was subsequently self-assembled with functionalized fullerenes via axial coordination and crown ether-alkyl ammonium cation complexation to form the donor-acceptor pairs, mimicking the noncovalently bound entities of the photosynthetic reaction center. The adopted self-assembly methodology yielded supramolecular complexes of higher stability, with defined geometry and orientation. Efficient forward electron transfer from the singlet excited zinc porphyrin dimer to the fullerene entity and relatively slow reverse electron transfer, important steps in the photosynthetic light energy conversion have been achieved in these novel biomimetic model systems.

Dimerization↗

Dimerization and double proton transfer-induced tautomerism of 4(3H)-pyrimidinone in solution studied by IR spectroscopy and quantum chemical calculations.

The tautomerism and dimerization of 4(3H)-pyrimidinone (4(3H)Pyr) in carbon tetrachloride (CCl4) and chloroform (CHCl3) solutions were investigated using IR spectroscopy and quantum chemical calculations. The observed IR spectra in the NH and OH stretching regions clearly revealed the predominance of the keto tautomer in both solvent systems. The enol form only exists in a very small proportion in the CCl4 solution. The tautomeric constant for the two monomers KT[OH/NH] = 0.012 and DeltaE = 2.62 kcal/mol were estimated at 25 degrees C. This result was supported by the self-consistent reaction field/polarizable continuum (SCRF/PCM) calculation at the MP4(full, SDQ)/aug-cc-pVDZ level, which predicted DeltaE = 3.06 kcal/mol in CCl4. In the C=O stretching region, two bands were observed, suggesting the coexistence of two keto structures at equilibrium. The calculated IR spectra indicated that the bands at 1711 and 1675 cm(-1) arise from the keto monomer and keto-keto (KK) ring dimer, respectively. At elevated temperature, the populations of both the keto and enol monomers increased for the CCl4 solution. The present study revealed that the keto <--> enol tautomerization does not occur in the isolated monomer molecule. The double proton transfer (DPT) reaction in the KK ring dimer presumably plays a substantial role in the population increase of the enol monomer. To our knowledge, this may be the first observation of the tautomerization in a model base pair via the temperature-induced ground-state DPT reaction under a nonpolar liquid environment reported so far. This tautomerism can serve as a mimic circumstance for the spontaneous mutations induced by proton transfer in the DNA base pairs.

Dimerization↗