52 research outputs found
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Enzyme-catalyzed cationic epoxide rearrangements in quinolone alkaloid biosynthesis.
Epoxides are highly useful synthons and biosynthons for the construction of complex natural products during total synthesis and biosynthesis, respectively. Among enzyme-catalyzed epoxide transformations, a reaction that is notably missing, in regard to the synthetic toolbox, is cationic rearrangement that takes place under strong acid. This is a challenging transformation for enzyme catalysis, as stabilization of the carbocation intermediate upon epoxide cleavage is required. Here, we discovered two Brønsted acid enzymes that can catalyze two unprecedented epoxide transformations in biology. PenF from the penigequinolone pathway catalyzes a cationic epoxide rearrangement under physiological conditions to generate a quaternary carbon center, while AsqO from the aspoquinolone pathway catalyzes a 3-exo-tet cyclization to forge a cyclopropane-tetrahydrofuran ring system. The discovery of these new epoxide-modifying enzymes further highlights the versatility of epoxides in complexity generation during natural product biosynthesis
Tackling unemployment in China: state capacity and governance issues
This paper considers China's state capacity and changing governance as revealed through its policies to tackle unemployment. Despite high levels of growth, economic restructuring has resulted in rising unemployment over the last decade. The Chinese state has been able to manage job losses from state enterprises, demonstrating some state capacity in relation to this sector and some persistent command economy governance mechanisms. However both design and implementation of policies to compensate and assist particular groups among the unemployed have been shaped by weak state capacity in several other areas. First, capacity to gather accurate employment data is limited, meaning local and central governments do not have a good understanding of the extent and nature of unemployment. Second, the sustainability of supposedly mandatory unemployment insurance schemes is threatened by poor capacity to enforce participation. Third, poor central state capacity to ensure local governments implement policies effectively leads to poor unemployment insurance fund capacity, resulting in provision for only a narrow segment of the unemployed and low quality employment services. Although the adoption of unemployment insurance (and its extension to employers and employees in the private sector), the introduction of a Labour Contract Law in 2007, and the delivery of employment services by private businesses indicate a shift towards the use of new governance mechanisms based on entitlement, contract and private sector delivery of public-sector goods, that shift is undermined by poor state capacity in relation to some of these new mechanisms
Recommended from our members
Enzyme-catalyzed cationic epoxide rearrangements in quinolone alkaloid biosynthesis.
Epoxides are highly useful synthons and biosynthons for the construction of complex natural products during total synthesis and biosynthesis, respectively. Among enzyme-catalyzed epoxide transformations, a reaction that is notably missing, in regard to the synthetic toolbox, is cationic rearrangement that takes place under strong acid. This is a challenging transformation for enzyme catalysis, as stabilization of the carbocation intermediate upon epoxide cleavage is required. Here, we discovered two Brønsted acid enzymes that can catalyze two unprecedented epoxide transformations in biology. PenF from the penigequinolone pathway catalyzes a cationic epoxide rearrangement under physiological conditions to generate a quaternary carbon center, while AsqO from the aspoquinolone pathway catalyzes a 3-exo-tet cyclization to forge a cyclopropane-tetrahydrofuran ring system. The discovery of these new epoxide-modifying enzymes further highlights the versatility of epoxides in complexity generation during natural product biosynthesis
Saroclazines A–C, thio-diketopiperazines from mangrove-derived fungi Sarocladium kiliense HDN11-84
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