Radiophotosynthesis of some 14C-labelled Amino Acids using the Unicellular Green Alga Scenedesmus acutus

Radiophotosynthesis has been carried out using the unicellular green algea Scenedesmus acutus grown, as a substrate for preparing some carbon-14 labelled amino acids. Gaseous ¹⁴CO₂, in an air tight photosynthesis chamber or NaH¹⁴CO₃ solution, in an ordinary photosynthesis chamber, were used as radioactive carbon sources. The yields, radiochemical yields and specific activities of the formed radioactive products are reported in both cases. The results obtained clearly showed the advantages of using the NaH¹⁴CO₃ method. In that case the process was by far less tedious. Moreover, the chemical and radiochemical yields of the formed amino acids were relatively much more higher than the values obtained on using ¹⁴CO₂ in the tight photosynthesis chamber.     

Updating Insights into the Catalytic Domain Properties of Plant Cellulose synthase (CesA) and Cellulose synthase-like (Csl) Proteins

The wall is the last frontier of a plant cell involved in modulating growth, development and defense against biotic stresses. Cellulose and additional polysaccharides of plant cell walls are the most abundant biopolymers on earth, having increased in economic value and thereby attracted significant interest in biotechnology. Cellulose biosynthesis constitutes a highly complicated process relying on the formation of cellulose synthase complexes. Cellulose synthase (CesA) and Cellulose synthase-like (Csl) genes encode enzymes that synthesize cellulose and most hemicellulosic polysaccharides. Arabidopsis and rice are invaluable genetic models and reliable representatives of land plants to comprehend cell wall synthesis. During the past two decades, enormous research progress has been made to understand the mechanisms of cellulose synthesis and construction of the plant cell wall. A plethora of cesa and csl mutants have been characterized, providing functional insights into individual protein isoforms. Recent structural studies have uncovered the mode of CesA assembly and the dynamics of cellulose production. Genetics and structural biology have generated new knowledge and have accelerated the pace of discovery in this field, ultimately opening perspectives towards cellulose synthesis manipulation. This review provides an overview of the major breakthroughs gathering previous and recent genetic and structural advancements, focusing on the function of CesA and Csl catalytic domain in plants.     

贵金属纳米颗粒的微生物合成

金属纳米颗粒在材料、催化、医学、环境等众多领域应用广泛,其中,金、银、铂、钯等贵金属的纳米颗粒作为良好的催化剂可提高反应的速率,因此,贵金属纳米颗粒的合成吸引了众多研究者的关注。传统的物理化学法虽能高效、可控地合成贵金属纳米颗粒,但是合成条件苛刻、成本昂贵、且会产生对环境有害的化学物质。因此,探索节能、环保、可持续的绿色合成方法成为纳米合成研究的热点之一。贵金属纳米颗粒的微生物合成法具备绿色合成技术的诸多要素,研究表明某些微生物能将金属盐转化成纳米材料,且微生物繁殖速度快、培养成本低、生长条件温和,从而得到了研究者们的广泛关注。本文归纳总结了目前微生物合成贵金属纳米颗粒的主要研究进展,包括贵金属纳米颗粒可能的合成机制以及尺寸与形貌控制方法,探讨了其在医学、催化、生物传感、环境方面的具体应用,并对贵金属纳米颗粒微生物合成的未来发展进行了展望。     

Scalable Biosynthesis of the Seaweed Neurochemical,Kainic Acid

Kainic acid, the flagship member of the kainoid family of natural neurochemicals, is a widely used neuropharmacological agent that helped unravel the key role of ionotropic glutamate receptors, including the kainate receptor, in the central nervous system. Worldwide shortages of this seaweed natural product in the year 2000 prompted numerous chemical syntheses, including scalable preparations with as few as six‐steps. Herein we report the discovery and characterization of the concise two‐enzyme biosynthetic pathway to kainic acid from l ‐glutamic acid and dimethylallyl pyrophosphate in red macroalgae and show that the biosynthetic genes are co‐clustered in genomes of Digenea simplex and Palmaria palmata. Moreover, we applied a key biosynthetic α‐ketoglutarate‐dependent dioxygenase enzyme in a biotransformation methodology to efficiently construct kainic acid on the gram scale. This study establishes both the feasibility of mining seaweed genomes for their biotechnological prowess.     

Bacterial Diterpene Biosynthesis

This Minireview summarises recent developments in the biosynthesis of diterpenes by diterpene synthases in bacteria. It is structured by the class of enzyme involved in the first committed step towards diterpenes, starting with type I diterpene synthases, followed by type II enzymes and the more recently discovered UbiA‐related diterpene synthases. A special emphasis lies on the reaction mechanisms of diterpene synthases that convert simple linear precursors through cationic cascades into structurally complex, usually polycyclic carbon skeletons with multiple stereogenic centres. A further main focus of this Minireview is a discussion of how these mechanisms can be unravelled. Downstream modifications to bioactive molecules are also covered.     

An Unusual Skeletal Rearrangement in the Biosynthesis of the Sesquiterpene Trichobrasilenol from Trichoderma

The skeletons of some classes of terpenoids are unusual in that they contain a larger number of Me groups (or their biosynthetic equivalents such as olefinic methylene groups, hydroxymethyl groups, aldehydes, or carboxylic acids and their derivatives) than provided by their oligoprenyl diphosphate precursor. This is sometimes the result of an oxidative ring‐opening reaction at a terpene‐cyclase‐derived molecule containing the regular number of Me group equivalents, as observed for picrotoxan sesquiterpenes. In this study a sesquiterpene cyclase from Trichoderma spp. is described that can convert farnesyl diphosphate (FPP) directly via a remarkable skeletal rearrangement into trichobrasilenol, a new brasilane sesquiterpene with one additional Me group equivalent compared to FPP. A mechanistic hypothesis for the formation of the brasilane skeleton is supported by extensive isotopic labelling studies.     

Triterpenes and limonoids of Cedrela: Distribution,biosynthesis, and 1H and 13C NMR data

Cedrela genus, a member of the Meliaceae family, presents both chemical characteristics associated with and those that distinguish it from the rest of its members. The presence of triterpenes and limonoids is the characteristic of the Meliaceae family, but the class and type of these chemical constituents are distinctive for each genus. Cedrela includes cycloartane, ursane, oleanane, tirucallane, butyrospermane, and apotirucallane triterpenes, and its limonoids belongs to six class and nine types, known as class Ia-type havanensines, class Ib-type delevoyin, class II-type gedunin, class IIIb-type andirobin, class IIIg-type mexicanolide, class IVa-type evoludone, class Va-type obacunol, class V-type limonin, and class VIII. Each of these structural arrangements includes specific traits, defined by their biosynthetic origin, which can be established by means of structural elucidation techniques, particularly ¹H and ¹³C NMR, which assisted by 2D NMR techniques, allowing to deduce their structures unequivocally. The constant presence of these skeletal arrangements in Cedrela ensures that they are its chemophenetic markers and their recurrence is an important criterion for their identity. This review is a compilation of the occurrence of triterpenes and limonoids in Cedrela genus, detailing their biosynthetic association and collecting and organizing their NMR data, with the purpose of facilitating its location, analysis, and use in the phytochemical study of species from this genus.     

Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo-Ring Formation with 8π-6π Electrocyclization

Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark.