Self-Assembly of Bidentate Ligands for Combinatorial Homogeneous Catalysis: Methanol-Stable Platforms Analogous to the Adenine–Thymine Base Pair

2007 ◽  
Vol 119 (17) ◽  
pp. 3097-3099 ◽  
Author(s):  
Christoph Waloch ◽  
Jörg Wieland ◽  
Manfred Keller ◽  
Bernhard Breit
Keyword(s):  
Homogeneous Catalysis ◽  
Base Pair ◽  
Self Assembly ◽  
Bidentate Ligands ◽  
Adenine Thymine

scholarly journals Self-Assembly of Bidentate Ligands for Combinatorial Homogeneous Catalysis: Asymmetric Rhodium-Catalyzed Hydrogenation.

ChemInform ◽  
2006 ◽  
Vol 37 (31) ◽  
Author(s):  
Martine Weis ◽  
Christoph Waloch ◽  
Wolfgang Seiche ◽  
Bernhard Breit
Keyword(s):  
Homogeneous Catalysis ◽  
Self Assembly ◽  
Bidentate Ligands

Self-Assembly of Bidentate Ligands for Combinatorial Homogeneous Catalysis:  Asymmetric Rhodium-Catalyzed Hydrogenation

2006 ◽  
Vol 128 (13) ◽  
pp. 4188-4189 ◽  
Author(s):  
Martine Weis ◽  
Christoph Waloch ◽  
Wolfgang Seiche ◽  
Bernhard Breit
Keyword(s):  
Homogeneous Catalysis ◽  
Self Assembly ◽  
Bidentate Ligands

Self-assembly of bidentate ligands for combinatorial homogeneous catalysis based on an A-T base pair model

2006 ◽  
Vol 78 (2) ◽  
pp. 249-256 ◽  
Author(s):  
Bernhard Breit ◽  
Wolfgang Seiche
Keyword(s):  
Hydrogen Bonding ◽  
Metal Complex ◽  
Base Pair ◽  
Self Assembly ◽  
Bidentate Ligands ◽  
Metal Complex Catalysis ◽  
System A ◽  
Pair Model ◽  
Excellent Activity ◽  
Monodentate Ligands

A new concept for generation of chelating ligand libraries for homogeneous metal complex catalysis based on self-assembly is presented. Thus, self-assembly of structurally simple monodentate ligands in order to give structurally more complex bidentate ligands is achieved employing hydrogen bonding. Based on this concept and on the 2-pyridone/hydroxypyridine tautomeric system, a new rhodium catalyst was identified which operated with excellent activity and regioselectivity upon hydroformylation of terminal alkenes. In order to generate defined unsymmetrical heterodimeric ligands, an A-T base pair analog-the aminopyridine/isoquinolone system-was developed which allows for complementary hydrogen bonding. Based on this platform, a 4 x 4 phosphine ligand library was screened in the course of the rhodium-catalyzed hydroformylation of 1-octene. A catalyst operating with outstanding activity and regioselectivity in favor of the linear aldehyde was discovered.

scholarly journals Ultrafast deactivation processes in the 2-aminopyridine dimer and the adenine-thymine base pair: Similarities and differences

2010 ◽  
Vol 133 (6) ◽  
pp. 064302 ◽  
Author(s):  
Yue-Jie Ai ◽  
Feng Zhang ◽  
Gang-Long Cui ◽  
Yi Luo ◽  
Wei-Hai Fang
Keyword(s):  
Base Pair ◽  
Similarities And Differences ◽  
Adenine Thymine

scholarly journals The fidelity of replication of the three-base-pair set adenine/thymine, hypoxanthine/cytosine and 6-thiopurine/5-methyl-2-pyrimidinone with T7 DNA polymerase

2004 ◽  
Vol 381 (3) ◽  
pp. 709-717 ◽  
Author(s):  
Harry P. RAPPAPORT
Keyword(s):  
Dna Polymerase ◽  
Rate Constant ◽  
Base Pair ◽  
Apparent Rate Constant ◽  
Polymerase Activity ◽  
Exonuclease Activity ◽  
Base Pairs ◽  
Error Frequency ◽  
Steady State Kinetics ◽  
Adenine Thymine

With the goal of constructing a genetic alphabet consisting of a set of three base pairs, the fidelity of replication of the three base pairs TH (5-methyl-2-pyrimidinone)/HS (6-thiopurine; thiohypoxanthine), C/H (hypoxanthine) and T/A was evaluated using T7 DNA polymerase, a polymerase with a strong 3′→5′ exonuclease activity. An evaluation of the suitability of a new base pair for replication should include both the contribution of the fidelity of a polymerase activity and the contribution of proofreading by a 3′→5′ exonuclease activity. Using a steady-state kinetics method that included the contribution of the 3′→5′ exonuclease activity, the fidelity of replication was determined. The method determined the ratio of the apparent rate constant for the addition of a deoxynucleotide to the primer across from a template base by the polymerase activity and the rate constant for removal of the added deoxynucleotide from the primer by the 3′→5′ exonuclease activity. This ratio was designated the eni (efficiency of net incorporation). The eni of the base pair C/H was equal to or greater than the eni of T/A. The eni of the base pair TH/HS was 0.1 times that of A/T for TH in the template and 0.01 times that of A/T for HS in the template. The ratio of the eni of a mismatched deoxynucleotide to the eni of a matched deoxynucleotide was a measure of the error frequency. The error frequencies were as follows: thymine or TH opposite a template hypoxanthine, 2×10−6; HS opposite a template cytosine, <3×10−4. The remaining 24 mismatched combinations of bases gave no detectable net incorporation. Two mismatches, hypoxanthine opposite a template thymine or a template TH, showed trace incorporation in the presence of a standard dNTP complementary to the next template base. T7 DNA polymerase extended the primer beyond each of the matched base pairs of the set. The level of fidelity of replication of the three base pairs with T7 DNA polymerase suggests that they are adequate for a three-base-pair alphabet for DNA replication.

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