An Iterative O‐Methyltransferase Catalyzes 1,11‐Dimethylation of Aspergillus fumigatus Fumaric Acid Amides

S‐adenosyl‐l ‐methionine (SAM)‐dependent methyltransfer is a common biosynthetic strategy to modify natural products. We investigated the previously uncharacterized Aspergillus fumigatus methyltransferase FtpM, which is encoded next to the bimodular fumaric acid amide synthetase FtpA. Structure elucidation of two new A. fumigatus natural products, the 1,11‐dimethyl esters of fumaryl‐l ‐tyrosine and fumaryl‐l ‐phenylalanine, together with ftpM gene disruption suggested that FtpM catalyzes iterative methylation. Final evidence that a single enzyme repeatedly acts on fumaric acid amides came from an in vitro biochemical investigation with recombinantly produced FtpM. Size‐exclusion chromatography indicated that this methyltransferase is active as a dimer. As ftpA and ftpM homologues are found clustered in other fungi, we expect our work will help to identify and annotate natural product biosynthesis genes in various species.     

Efficient Engineering and Production Concepts for Products in Regulated Environments – Dream or Nightmare?

Manufacturing of chemical‐pharmaceutical products is moving increasingly fast on a global scale. Therefore, developing and starting up production facilities fast, with high quality, and at reasonable costs has become extremely challenging. Engineering concepts like modularization, standardization and simultaneous/parallel engineering are discussed as methods for speeding up process design and filing for regulatory approval. Transfer from batch to continuous operation mode of production is pointed out as the key‐issue in such strategies.     

Development and Evaluation of a Nanoparticle Generator for Human Inhalation Studies with Airborne Zinc Oxide

In the EU there is an increasing need for regulatory agencies to derive health based threshold limits based on human inhalation studies with airborne particles. A necessary prerequisite for such projects is the development of a suitable generator system to produce nanoparticle test aerosols for human whole-body inhalation studies. We decided to use a generator with flame-based heating of aqueous precursor solutions. Validation of the test system was done by generating zinc oxide (ZnO) nanoparticles with minimal contamination of trace gases, i.e., nitric oxides or carbon monoxide that could confound the effects seen in exposed subjects. ZnO was selected based on the uncertainties surrounding its health effects after exposure at the workplace. The generation process of the developed flame generator yields ZnO nanoparticles with monomodal size distribution and very good temporal stability. The maximum target exposure mass concentration of 2 mg/m³ ZnO, with a resulting median particle diameter of 57 nm, is attainable in our human exposure laboratory. The morphological examination shows typical agglomerates and aggregates formed by high temperature processes. Overall, the performed experiments confirm that a constant exposure can be provided for all subjects at all times.

Copyright 2014 American Association for Aerosol Research     

13C-NMR Spectroscopic Detection of Malto-oligosaccharide Complexes

Fragments of amylose were enzymatically synthesized and purified to α-(a→4)-glucans of well defined degress of polymerization by preparative size exclusion chromatography. Maltooligosaccharides from DP 3 to 12 were subjected to ¹³C-NMR-spectroscopy. The addition of iodine as a complexing agent selectively affected the carbon atoms involved in the glycosidic bond. Resonances of C-1 and C-4 experienced a dramatic downfield shift. This is interpreted as a change of conformation of the amylose helix. The shift differences can be measured conveniently and be used for calculations of complex stability constants. Maltohexaose and higher saccharides gave strong effects upon complexation, indicating that one helical turn brings about a gain in helical stability. No lower chain-length limit for the complex-forming capacity was observed. Even the smallest fragments of amylose showed complexing behaviour.     

Pre-adolescent children exhibit lower aerosol particle volume emissions than adults for breathing,speaking, singing and shouting

Speaking and singing are activities linked to increased aerosol particle emissions from the respiratory system, dependent on the utilized vocal intensity. As a result, these activities have experienced considerable restrictions in enclosed spaces since the onset of the COVID-19 pandemic due to the risk of infection from the SARS-CoV-2 virus, transmitted by virus-carrying aerosols. These constraints have affected public education and extracurricular activities for children as well, from in-person music instruction to children’s choirs. However, existing risk assessments for children have been based on emission measurements of adults. To address this, we measured the particle emission rates of 15 pre-adolescent children, all eight to ten years old, with a laser particle counter for the test conditions: breathing at rest, speaking, singing and shouting. Compared with values taken from 15 adults, emission rates for breathing, speaking and singing were significantly lower for children. Particle emission rates were reduced by a factor of 4.3 across all conditions, whereas emitted particle volume rates were reduced by a factor of 4.8. These data can supplement SARS-CoV-2 risk management scenarios for various school and extracurricular settings.     

生物聚合物的创新应用

描述了生物聚合物的创新应用.探索了两种趋势的原因.首先,最近三年中,原油价格猛涨,各种衍生物的价格也随之上涨,促使人们寻找其他可能的原料.其次,欧洲农业处于重大变革的前夜,环境法律的实施,向世界经济的开放以及补贴的减少,促使农业寻找新的市场.玉米和糖用甜菜可能是未来的出路.     

Photochemie von Acylaziden. VIII [1]. Reagieren Acylnitrene wie 1,3-Dipole??

Photochemistry of Acylazides. VIII. Do Acylnitrenes React like 1,3-Dipoles? The formation of three- ore five-membered heterocyclic rings by the reaction of acylnitrenes with olefins depends on the electron density at the double bond. The generally expected formation of aziridines by a cheletropic reaction was observed by photolysis of aroylazides 1 in the presence of 2,5-dihydrofuran 2 . But with enolethers 3 and 4 oxazolines were directly formed. This [3 + 2] cycloaddition is regiospecific. The cycloaddition is modestly stereoselective by steric hindrance within the cyclic enolether 3b . Very small de-values were found with chiral substituents in the acylazide 13 . The azide decomposition was also achieved by photoinduced electron transfer. The same cycloaddition products as obtained by direct photolysis of the azides were obtained via radical anions of the acylazide. Using Michler's ketone as electron donor in the triplet state the formation of isocyanate which diminishes the yield of cycloadducts can be avoided.