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Perrin, Charles L.,Lau, Jonathan S.,Kim, Yeong-Joon,Karri, Phaneendrasai,Moore, Curtis,Rheingold, Arnold L. American Chemical Society 2009 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.131 No.37
<P>The large pK(a) difference between first and second deprotonations of (+/-)-alpha,alpha'-di-tert-butylsuccinic acid has been interpreted as evidence for a short, strong intramolecular hydrogen bond in the monoanion. Incorporation of (18)O into one carboxyl group allows investigation of the symmetry of the H-bond in solution by the method of isotopic perturbation. Relative to the intrinsic (18)O-induced isotope shift at the carboxyl carbon, as measured in the diacid, an additional isotope shift of 8 ppb in methanol, 14 ppb in acetone, and 5 ppb in THF is observed for potassium hydrogen (+/-)-alpha,alpha'-di-tert-butylsuccinate-(18)O. This increase indicates that the ion exists as an equilibrating pair of interconverting tautomers and not as a single symmetric resonance hybrid. The X-ray crystal structures of the tetrapropylammonium, tetrabutylammonium, tetrabutylphosphonium, magnesium, and calcium hydrogen (+/-)-alpha,alpha'-di-tert-butylsuccinate salts show a remarkably short O-O distance of 2.41 A, consistent with a strong hydrogen bond. However, the dicesium salt of the (+/-)-alpha,alpha'-di-tert-butylsuccinate dianion also shows the short O-O distance of 2.41 A, so this cannot be taken as evidence for a strong hydrogen bond in the monoanion. Moreover, the two O-H distances in the monoanions are unequal, and the hydrogen bond is asymmetric in these crystals. It is concluded that there is no evidence for any special stabilization associated with symmetric H-bonds. The large Delta pK(a) difference is therefore not due to any feature of the H-bond itself but is attributed to the electrostatic repulsion between the carboxylates in the dianion, which is relieved in the monoanion by inserting a proton between the carboxylates.</P>
Walley, Peter G.,Teakle, Graham R.,Moore, Jonathan D.,Allender, Charlotte J.,Pink, David A.C.,Buchanan-Wollaston, Vicky,Barker, Guy C. The Korean Society of Plant Biotechnology 2012 식물생명공학회지 Vol.39 No.1
The vegetable brassicas are an important crop worldwide and are of significant commercial value. In order to ensure our targets for food security are met it is important that these crops are continually improved to increase sustainability of production, increase nutritional quality and reduce waste. Development of resistances against both biotic and abiotic stress are recognised as being key. Plant breeding plays a vital role in addressing these issues through the development of new and improved varieties. This continued improvement is becoming evermore dependent on our ability to identify and introgress beneficial alleles from 'exotic' germplasm into elite breeding material. Increasingly, more diverse germplasm such as those found in genebanks is being screened for benificial allelic variation, however, plant breeders often find it difficult to make use of such material due to the time required to remove undesirable characteristics from progeny due to linkage drag. This article describes how we have attempted to overcome this and develop resources that make the diversity available within the $Brassica$ $oleracea$ genepool more accessible.
Peter G Walley,Graham R Teakle,Jonathan D Moore,Charlotte J Allender,Vicky Buchanan-Wollaston,David AC Pink,Guy C Barker 한국식물생명공학회 2012 식물생명공학회지 Vol.39 No.1
The vegetable brassicas are an important crop worldwide and are of significant commercial value. In order to ensure our targets for food security are met it is important that these crops are continually improved to increase sustainability of production, increase nutritional quality and reduce waste. Development of resistances against both biotic and abiotic stress are recognised as being key. Plant breeding plays a vital role in addressing these issues through the development of new and improved varieties. This continued improvement is becoming evermore dependent on our ability to identify and introgress beneficial alleles from ‘exotic’ germplasm into elite breeding material. Increasingly, more diverse germplasm such as those found in genebanks is being screened for benificial allelic variation, however, plant breeders often find it difficult to make use of such material due to the time required to remove undesirable characteristics from progeny due to linkage drag. This article describes how we have attempted to overcome this and develop resources that make the diversity available within the Brassica oleracea genepool more accessible.
Anguera, Gonzalo,Cha, Won-Young,Moore, Matthew D.,Lee, Juhoon,Guo, Shenyi,Lynch, Vincent M.,Kim, Dongho,Sessler, Jonathan L. American Chemical Society 2018 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.140 No.11
<P>A new expanded porphyrin, hexadecaphyrin-(1.0.0.0.1.1.0.1.1.0.0.0.1.1.0.1), is reported. It was obtained via the condensation of a hexapyrrolic derivative prepared in turn from a bipyrrole dialdehyde and a stable quaterpyrrole precursor. This hexadecaphyrin contains eight direct α-pyrrole-to-α-pyrrole linkages in its structure. It supports the formation of bimetallic complexes of both zinc and cobalt that are characterized by different conformational structures. Furthermore, a mixed zinc/cobalt macrocycle has been prepared. The cobalt bimetallic complex shows two stable conformations with the same oxidation state that are in equilibrium. All compounds have been characterized by common spectroscopic means, and single crystal X-ray diffraction structures were obtained for all macrocyclic compounds. DFT calculations and transient absorption spectra were used to study the electronic features of the complexes and the effect of conformational changes. This system shows promise as an accumulated heat sensor.</P> [FIG OMISSION]</BR>