Theoretical calculation of electrode potentials: Electron-withdrawing compounds

The electrode potential of 2,3-dicyanobenzoquinone in aqueous solution has been calculated relative to parabenzoquinone using a thermodynamic cycle approach that includes accurate gasphase ab initio calculations and calculation of differences in free energies of hydration using the free-energy perturbation method. The discrepancy between the calculated and experimental electrode potential is disappointingly large (99 mV) compared to previous studies using this approach. This, along with the experimental evidence, suggests that the experimental value itself is too large and that theoretical approaches may indeed be as reliable as experimental ones for determining redox properties of molecules such as 2,3-dicyanobenzoquinone. In the light of this discrepancy we have examined the variation of the results with the basis set, inclusion of electron correlation and changes in the parameters used in the molecular dynamics free-energy simulations. The results are shown to be dependent upon the torsional parameters and especially dependent upon the basis set or semiempirical method used to obtain the electrostatic potential-derived charges. The best charge set was determined using the ab initio criteria of completeness—as far as it can be applied to large molecules—and also by studying the effect of hydration on these charges. This was done by allowing the solvent to perturb the wave function prior to the electrostatic potential determination. Thus, 3-21G and 6-31G * basis sets were found to give satisfactory results. Similar results were obtained using semiempirical and ab initio geometries.     

Synthesis of 2,2′-bipyrrole-5-carboxaldehydes and their application in the synthesis of B-ring functionalized prodiginines and tambjamines

Facile, versatile, and cost-effective synthetic routes for the preparation of a range of new 3-alkyl-, 4-alkyl-, 3,4-dialkyl-, and 3-halo-4-alkyl-2,2′-bipyrrole-5-carboxaldehydes have been developed. These 2,2′-bipyrrole-5-carboxaldehydes offer interesting potential as building blocks for making bioactive natural and unnatural products, as demonstrated by the synthesis of B-ring functionalized prodiginines (PGs) and tambjamines.     

Structural studies of metal ligand complexes by ion mobility-mass spectrometry

Collision cross sections (CCS) have been measured for three salen ligands, and their complexes with copper and zinc using travelling-wave ion mobility-mass spectrometry (TWIMS) and drift tube ion mobility-mass spectrometry (DTIMS), allowing a comparative size evaluation of the ligands and complexes. CCS measurements using TWIMS were determined using peptide and TAAH calibration standards. TWIMS measurements gave significantly larger CCS than DTIMS in helium, by 9 % for TAAH standards and 3 % for peptide standards, indicating that the choice of calibration standards is important in ensuring the accuracy of TWIMS-derived CCS measurements. Repeatability data for TWIMS was obtained for inter- and intra-day studies with mean RSDs of 1.1 % and 0.7 %, respectively. The CCS data obtained from IM-MS measurements are compared to CCS values obtained via the projection approximation, the exact hard spheres method and the trajectory method from X-ray coordinates and modelled structures using density functional theory (DFT) based methods.     

The statistical significance of selected sense–antisense peptide interactions

Sense and antisense peptides, encoded by sense and corresponding antisense DNA strands, are capable of specific interactions that could be a driving force to mediate protein–protein or protein–peptide binding associations. The complementary residue hypothesis suggests that these interactions are founded upon the sum of pairwise interactions between amino acids encoded by corresponding sense and antisense codons. Despite many successful experimental results obtained with the hypothesis, however, the physicochemical basis for these interactions is poorly understood. We examined the potential of the hypothesis for general identification of protein–protein interaction sites, and the possible role of the hypothesis in determining folding in a broad set of protein structures. In addition, we performed a structural study to investigate the binding of a complementary peptide to IL‐1F2. Our results suggest that complementary residue pairs are no more frequent or conserved than average in protein–protein interfaces, and are statistically under‐represented amongst contacting residue pairs in folded protein structures. Although our structural results matched experimental observations of binding between the peptide and IL‐1F2, complementary residue interactions do not appear to be dominant in the bound structure. Overall, our data do not allow us to conclude that the complementary residue hypothesis accounts for specific sense–antisense peptide interactions. © 2012 Wiley Periodicals, Inc.     

Novel Bis-arylPheDOT Synthons for Electrochromic Polymers

Two terthiophenes incorporating the synthon 3,4-(1,2-phenylenedioxy)thiophene (PheDOT) have been developed. Specifically, 2,5-bisthienyl-3,4-(1,2-phenylenedioxy)thiophene (BTh-PheDOT 1) and 2,5-bisethylenedioxythienyl-3,4-(1,2-phenylenedioxy)thiophene (BEDOT-PheDOT 2) were electropolymerized to form electroactive polymer films (P1 and P2) that switched between two highly colored states with the more electron-rich EDOT derivative P2 observed to switch at a lower potential. Additionally, both P1 and P2 displayed moderate to low optical bandgaps of 1.8 and 1.6 eV, respectively. Crystal structures of BTh-PheDOT showed the monomer to be nearly planar with π -stacking observable between monomers. These findings demonstrate the potential of PheDOT as an electroactive synthon for the formation of well-ordered systems.     

A Short and Efficient Stereoselective Synthesis of the Potent 5-Lipoxygenase Inhibitor CMI-977

A short and efficient synthesis of the potent 5-lipoxygenase inhibitor CMI-977 is described using as the key step a stereoselective anomeric oxygen to carbon rearrangement of an alkynyl stannane tetrahydrofuranyl ether derivative mediated by boron trifluoride etherate.