bis-cis-dihydrodiols: A new class of metabolites resulting from biphenyl dioxygenase-catalyzed sequential asymmetric cis-dihydroxylation of polycyclic arenes and heteroarenes

The biphenyl dioxygenase-catalyzed asymmetric mono-cis-dihydroxylation of the tetracyclic arenes chrysene 1A, benzo[c]phenanthridine 1B, and benzo[b]naphtho[2,1-d]thiophene 1C, has been observed to occur exclusively at the bay or pseudo-bay region using the bacterium Sphingomonas yanoikuyae B8/36. The mono-cis-dihydrodiol derivatives 2A and 2C, obtained from chrysene 1A by oxidation at the 3,4-bond (2A) and benzo[b]naphtho[2,1-d]thiophene 1C by oxidation at the 1,2-bond (2C), respectively, have been observed to undergo a further dioxygenase-catalyzed asymmetric cis-dihydroxylation at a second bay or pseudo-bay region bond to yield the corresponding bis-cis-dihydrodiols (cis-tetraols) 4A and 4C, the first members of a new class of microbial metabolites in the polycyclic arene series. The enantiopurities and absolute configurations of the new mono-cis-dihydrodiols 2B, 2C, and 3B were determined by H-1 NMR analyses of the corresponding (R)- and (S)-2-(1-methoxyethyl)benzeneboronate (MPBA) ester derivatives. The structure and absolute configurations of the bis-cis-dihydrodiols 4A and 4C were unambiguously determined by spectral analyses, stereochemical correlations, and, for the metabolite 4C, X-ray crystallographic analysis of the bis-acetonide derivative 7C. These results illustrate the marked preference of biphenyl dioxygenase for the cis-di- and tetra-hydroxylations of polycyclic arenes, at the more hindered bay or pseudo-bay regions, by exclusive addition from the same (si:si) face, to yield single enantiomers containing two and four chiral centers.

A new landscape of arts-based buildings and comparative cultural policies on the island of Ireland: the curse of Jocasta's necklace

Much current cultural policy research focuses on activity traditionally viewed as arts practice: visual arts, music, literature and dance. Architecture’s role in the discussion of cultural policy is, however, less certain and thus less frequently interrogated. The study presented here both addresses this dearth of in-depth research while also contributing to the interdisciplinary discussion of cultural policy in wider terms. In seeking to better understand how architectural culture is regulated and administered in a specific case study, it unpacks how the complicated relationships of nominal and explicit policies on both sides of the Irish/Northern Irish border contributed to the significant expansion of arts-based buildings 1995-2008. It contrasts political and cultural motivations behind these projects during a period of significant economic growth, investment and inward immigration. Data has been gathered from both official published policies as well as interviews with elite actors in the decision-making field and architects who produced the buildings of interest in both countries. With the sizeable number of arts-based buildings now completed in both Republic of Ireland and Northern Ireland, one must wonder if this necklace of buildings is, like Jocasta’s, a thing of both beauty and redolent with a potential future curse. It is the goal of this project to contribute to the larger applied and critical discussion of these issues and to engage with future policy design, administration and, certainly, evaluation.

The Bonds of Brotherhood: New Evidence of Sino-North Korean Exchanges, 1950-1954

Drawing on recently declassified documents from the archive of the Foreign Ministry of the People’s Republic of China (PRC), this article looks at China’s relationship with North Korea during and immediately after the Korean War. Although previous scholarship has touched on PRC–North Korean military ties during the war, this article is the first in-depth analysis of issues that are less well understood, notably China’s efforts to cope with a huge influx of refugees from North Korea, the PRC’s economic assistance during the war and in the early postwar reconstruction, and Chinese educational and ideological support for North Korean professionals and party cadres. The article shows that the extensive military coordination between Beijing and Pyongyang was only one way in which the war brought North Korea and the PRC into a closer relationship