From Isonitriles to Unsaturated NHC Complexes of Gold,Palladium and Platinum

In a modular template synthesis, unsaturated NHC complexes of gold, palladium and platinum were synthesized from simple metal salts, isonitriles and amines with acetal or ketal groups. Upon the addition of amines with tethered acetal or ketal moieties to the metal‐activated isonitrile, first nitrogen acyclic carbene (NAC) complexes are formed. These undergo ring closure and elimination to the unsaturated NHC complexes upon addition of acid. This simple strategy opens an attractive and fast approach to NHC complexes of gold, palladium and platinum. The modular approach allows a fast modification and is well‐suited for the synthesis of unsymetrically and symmetrically substituted unsaturated NHC complexes.

     

Unraveling the Dynamic Nanoscale Reducibility (Ce4+ → Ce3+) of CeOx–Ru in Hydrogen Activation

The interaction of molecular hydrogen with ceria is of important relevance for heterogeneous catalysis related to green chemistry and renewable energy. Here, the complex structural transformations of a well‐defined cerium oxide model catalyst are followed in situ and in real time when exposed to a reactive H₂ environment. By using electron spectromicroscopy and diffraction with chemical and structural sensitivities, it is demonstrated that the transition from CeO₂ to crystalline Ce₂O₃ occurs through a mixture of transient, coexisting phases on the nanoscale. The findings establish a clear relationship between structure and functionality for hydrogen dissociation over ceria(111), bearing profound implications on the nature of the reduction (Ce⁴⁺ → Ce³⁺) and mechanism for H₂ scission.     

Vacuolar and extracellular maturation of Saccharomyces cerevisiae proteinase A

The vacuolar aspartyl protease proteinase A (PrA) of Saccharomyces cerevisiae is encoded as a preproenzyme by the PEP4 gene and transported to the vacuole via the secretory route. Upon arrival of the proenzyme proPrA to the vacuole, active mature 42 kDa PrA is generated by specific proteolysis involving the vacuolar endoprotease proteinase B (PrB). Vacuolar activation of proPrA can also take place in mutants lacking PrB activity (prb1). Here an active 43 kDa species termed pseudoPrA is formed, probably by an autocatalytic process. When the PEP4 gene is overexpressed in wild-type cells, mature PrA can be found in the growth medium. We have found that prb1 strains overexpressing PEP4 can form pseudoPrA extracellularly. N-terminal amino acid sequence determination of extracellular, as well as vacuolar pseudoPrA showed that it contains nine amino acids of the propeptide, indicating a cleavage between Phe67 and Ser68 of the preproenzyme. This cleavage site is in accordance with the known substrate preference for PrA, supporting the notion that pseudoPrA is formed by autoactivation. When a multicopy PEP4 transformant of a prb1 mutant was grown in the presence of the aspartyl protease inhibitor pepstatin A, a significant level of proPrA was found in the growth medium. Our analyses show that overexpression of PEP4 leads to the secretion of proPrA to the growth medium where the zymogen is converted to pseudoPrA or mature PrA in a manner similar to the vacuolar processing reactions. Amino acid sequencing of secreted proPrA confirmed the predicted cleavage by signal peptidase between Ala22 and Lys23 of the preproenzyme.     

均方根值——平均值检波器——一种脉冲干扰抑制效果更佳的新型CISPR加权检波器

阐述了加权的目的,给出了新型均方根值(RMS)——平均值(AV)检波器的加权特性评估和加权函数的定义。同时对使用准峰值和平均值检波方式所得到的测量结果与使用均方根值—平均值检波方式所得到的测量结果进行了比较。根据比较结果,提出了均方根值——平均值检波方式所对应的发射类测试限值的建议。     

Bioraffinerien auf Basis schwach verholzter Biomasse

Weakly lignified biomass, like brewers' spent grain and grass silage, is good feedstock for biorefineries. The biomass can be separated and converted into valuable products in different ways. In this study, brewers' spent grain is used to investigate solid state fermentations with Cellulomonas uda. Additionally, hydrothermal pretreatment and subsequent enzymatic saccharification, as well as formation of inhibitory compounds, is demonstrated. Hydrothermal pretreatment combined with simultaneous saccharification and fermentation is shown as an example for the utilization of grass silage.     

Aurora Kinase A Is Involved in Controlling the Localization of Aquaporin-2 in Renal Principal Cells

The cAMP-dependent aquaporin-2 (AQP2) redistribution from intracellular vesicles into the plasma membrane of renal collecting duct principal cells induces water reabsorption and fine-tunes body water homeostasis. However, the mechanisms controlling the localization of AQP2 are not understood in detail. Using immortalized mouse medullary collecting duct (MCD4) and primary rat inner medullary collecting duct (IMCD) cells as model systems, we here discovered a key regulatory role of Aurora kinase A (AURKA) in the control of AQP2. The AURKA-selective inhibitor Aurora-A inhibitor I and novel derivatives as well as a structurally different inhibitor, Alisertib, prevented the cAMP-induced redistribution of AQP2. Aurora-A inhibitor I led to a depolymerization of actin stress fibers, which serve as tracks for the translocation of AQP2-bearing vesicles to the plasma membrane. The phosphorylation of cofilin-1 (CFL1) inactivates the actin-depolymerizing function of CFL1. Aurora-A inhibitor I decreased the CFL1 phosphorylation, accounting for the removal of the actin stress fibers and the inhibition of the redistribution of AQP2. Surprisingly, Alisertib caused an increase in actin stress fibers and did not affect CFL1 phosphorylation, indicating that AURKA exerts its control over AQP2 through different mechanisms. An involvement of AURKA and CFL1 in the control of the localization of AQP2 was hitherto unknown.     

Extraction of heavy metals from soils using biodegradable chelating agents

Metal pollution of soils is widespread across the globe, and the clean up of these soils is a difficulttask. One possible remediation technique is ex-situ soil washing using chelating agents. Ethylenediaminetetraacetic acid (EDTA) is a very effective chelating agent for this purpose but has the disadvantage that it is quite persistent in the environment due to its low biodegradability. The aim of our work was to investigate the biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDSA), methylglycine diacetic acid (MGDA), and nitrilotriacetic acid (NTA) as potential alternatives and compare them with EDTA for effectiveness. Kinetic experiments showed for all metals and soils that 24 h was the optimum extraction time. Longer times only gave minor additional benefits for heavy metal extraction but an unwanted increase in iron mobilization. For Cu at pH 7, the order of the extraction efficiency for equimolar ratios of chelating agent to metal was EDDS > NTA> IDSA > MGDA > EDTA and for Zn it was NTA > EDDS > EDTA >MGDA > IDSA. The comparatively low efficiency of EDTA resulted from competition between the heavy metals and co-extracted Ca. For Pb the order of extraction was EDTA > NTA >EDDS due to the much stronger complexation of Pb by EDTA compared to EDDS. At higher concentration of complexing agent, less difference between the agents was found and less pH dependence. There was an increase in heavy metal extraction with decreasing pH, but this was offset by an increase in Ca and Fe extraction. In sequential extractions EDDS extracted metals almost exclusively from the exchangeable, mobile, and Mn-oxide fractions. We conclude that the extraction with EDDS at pH 7 showed the best compromise between extraction efficiency for Cu, Zn, and Pb and loss of Ca and Fe from the soil.     

The effect of cocoa fermentation and weak organic acids on growth and ochratoxin A production by Aspergillus species

The acidic characteristics of cocoa beans have influence on flavor development in chocolate. Cocoa cotyledons are not naturally acidic, the acidity comes from organic acids produced by the fermentative microorganisms which grow during the processing of cocoa. Different concentrations of these metabolites can be produced according to the fermentation practices adopted in the farms, which could affect the growth and ochratoxin A production by fungi. This work presents two independent experiments carried out to investigate the effect of some fermentation practices on ochratoxin A production by Aspergillus carbonarius in cocoa, and the effect of weak organic acids such as acetic, lactic and citric at different pH values on growth and ochratoxin A production by A. carbonarius and Aspergillus niger in culture media. A statistical difference (ρ<0.05) in the ochratoxin A level in the cured cocoa beans was observed in some fermentation practices adopted. The laboratorial studies demonstrate the influence of organic acids on fungal growth and ochratoxin A production, with differences according to the media pH and the organic acid present. Acetic acid was the most inhibitory acid against A. carbonarius and A. niger. From the point of view of food safety, considering the amount of ochratoxin A produced, fermentation practices should be conducted towards the enhancement of acetic acid, although lactic and citric acids also have an important role in lowering the pH to improve the toxicity of acetic acid.     

WSA-DC——下一代高浓度高转化率WSA工艺

介绍了托普索公司新开发的WSA-DC工艺,详述其流程、优点、性能、消耗和生产数据.WSA-DC工艺是一个两次冷凝工艺,它结合了WSA工艺与两转两吸工艺的优点,通过对中间冷凝器的设计改进和仔细控制气体中的H2O/SO2比率,可以用ψ(SO2)等于或高于13%的原料气生产w(H2SO4)为99%的硫酸.以1套540t/d硫磺制酸装置为例,对WSA-DC工艺和传统干法两转两吸工艺进行了技术经济比较.