41882-29-5Relevant academic research and scientific papers
Fuel-Driven Dynamic Combinatorial Libraries
Bergmann, Alexander M.,Boekhoven, Job,Kriebisch, Christine M. E.
, p. 7719 - 7725 (2021/05/26)
In dynamic combinatorial libraries, molecules react with each other reversibly to form intricate networks under thermodynamic control. In biological systems, chemical reaction networks operate under kinetic control by the transduction of chemical energy. We thus introduced the notion of energy transduction, via chemical reaction cycles, to a dynamic combinatorial library. In the library, monomers can be oligomerized, oligomers can be deoligomerized, and oligomers can recombine. Interestingly, we found that the dynamics of the library's components were dominated by transacylation, which is an equilibrium reaction. In contrast, the library's dynamics were dictated by fuel-driven activation, which is a nonequilibrium reaction. Finally, we found that self-assembly can play a large role in affecting the reaction's kinetics via feedback mechanisms. The interplay of the simultaneously operating reactions and feedback mechanisms can result in hysteresis effects in which the outcome of the competition for fuel depends on events that occurred in the past. In future work, we envision diversifying the library by modifying building blocks with catalytically active motifs and information-containing monomers.
Electrochemically Induced Dynamics of a Benzylic Amide [2]Catenane
Ceroni, Paola,Leigh, David A.,Mottier, Loiì?c,Paolucci, Francesco,Roffia, Sergio,Tetard, David,Zerbetto, Francesco
, p. 10171 - 10179 (2007/10/03)
The electrochemistry of a benzylic amide [2]catenane was investigated and compared to that of its topologically trivial components. The redox behavior of both the catenane and the uninterlocked macrocycle can be largely understood in terms of the electrochemistry of smaller molecular fragments and simple molecular orbital considerations that show that the electroactivity of the C=O groups is split into two sets of quasi-degenerate potentials separated by a substantial gap. A fast intermolecular reaction follows the reduction of the macrocycle and smaller fragments, consistent with the corresponding dimers containing a new C-C bond linking two reduced carbonyls. The cyclic voltammetric behavior of the catenane differs significantly from that of the macrocycle-a feature that must therefore be directly attributable to the mechanically interlocked molecular architecture of the catenane. In particular, an intramolecular reaction (irreversible in the CV time scale) occurs in the catenane, which is shown to be a function of temperature and scan rate. Simulation of the cyclic voltammograms shows that the intramolecular reaction occurs on a time scale wider than that of circumrotation of the two rings in the neutral molecule, thus excluding that cyclic voltammetry (CV) is monitoring the latter process. Both the analysis of the electrochemical data and semiempirical quantum chemical (MNDO) calculations would suggest that the electrochemically induced reaction in the catenane is the soldering of the two interlocked macrocycles: the formation of a C-C bond between two reduced carbonyl groups would thus prevent further rotation of the two interlocked rings.
Aromatic analogs of arcaine inhibit MK-801 binding to the NMDA receptor
Sharma, Terre A.,Carr, Andrew J.,Davis, Rebecca S.,Reynolds, Ian J.,Hamilton, Andrew D.
, p. 3459 - 3464 (2007/10/03)
Aromatic analogs of arcaine were shown to have inhibitory effects on the binding of the channel blocking drug [3H]MK-801 to the NMDA receptor complex. The most potent compound of the series was an N,N - bis(propyl)guanidinium which inhibited [3H]MK-801 binding with an IC50 of 0.58 μM and an IC50 of 12.17 μM upon addition of 100 μM spermidine. The increase in IC50 upon addition of spermidine suggests competitive antagonism between the inhibitor and spermidine at the arcaine-sensitive polyamine site of the NMDA receptor complex.
