Zur Existenzfähigkeit von 2-Imino-2H-1,3-thiazinen

On the Existence of 2-Imino-2H-1,3-thiazines The title compounds 2 are readily liberated from the 2-amino-1,3-thiazinium salts 1 by treatment with bases. Their stability depends sensitively on the substituents at the imino-N. The imino-N substituted 2a – i are isolable as well-defined coloured substances. Reaction of the 2 as well 1 with nucleophilic agents affords pyrimidine-2-thiones ( 4 , 9 – 11 , 16 – 18 ). In these ring transformations a nucleophilic addition at ring position 6 as primary reaction step is preferred. The imino-N unsubstituted representatives display a more complicated behaviour; the highly enhanced reactivity prevents or handicaps, respectively, any isolation. As exemplified in the base-induced ring-transformation of 1 m to the pyrimidine derivative 19 , these 2 are able to react as nucleophiles too, and versatile intermolecular self-reactions are increasingly favoured.     

广告业的国际标准

随着数据传送、接收全球化的发展,广告的国际化进程速度加快,要求有一个全球性标准。     

Synthesis and Reactivity of Iron(II) Complexes with a New Tripodal Imine Ligand

A new tripodal imine ligand tris(2-(propan-2-ylideneamino)ethyl)amine (imine₃tren) was prepared in order to stabilize high valent iron-oxido complexes. Iron complexes were synthesized in template reactions from iron(II) salts, tris(2-aminoethyl)amine (tren) and acetone. Due to the reversibility of the imine formation, complexes with different ligands were obtained depending on the reaction conditions. Three complexes, [Fe(imine₃tren)(OAc)₂] ( 1 ), [Fe(imine₃tren)(OAc)]OTf ( 2 ) and [(imine₃tren)₂Fe₂(F)₂](SbF₆)₂ ( 3 ), could be synthesized and structurally characterized. However, reactions with hydrogen peroxide, iodosobenzene or ozone did not lead to any kind of “oxygen adduct” complex that could be spectroscopically observed.     

Characterisation of CYP102A25 from Bacillus marmarensis and CYP102A26 from Pontibacillus halophilus: P450 Homologues of BM3 with Preference towards Hydroxylation of Medium‐Chain Fatty Acids

Cytochrome P450 monooxygenases are highly desired biocatalysts owing to their ability to catalyse a wide variety of chemically challenging C?H activation reactions. The CYP102A subfamily of enzymes are natural catalytically self‐sufficient proteins consisting of a haem and FMN‐FAD reductase domain fused in a single‐component system. They catalyse the oxygenation of saturated and unsaturated fatty acids to produce primarily ω?1, ω?2 and ω?3 hydroxy acids. These monooxygenases have potential applications in biotechnology; however, their substrate range is still limited and there is a continued need to add diversity to this class of biocatalysts. Herein, we present the characterisation of two new members of this class of enzymes, CYP102A25 (BMar) from Bacillus marmarensis and CYP102A26 (PHal) from Pontibacillus halophilus, both of which express readily in a recombinant bacterial host. BMar exhibits the highest activity toward myristic acid and shows moderate activity towards unsaturated fatty acids. PHal exhibits broader activity towards mid‐chain‐saturated (C₁₄–C₁₈) and unsaturated fatty acids. Furthermore, PHal shows good regioselectivity for the hydroxylation of myristic acid, targeting the ω?2 position for C?H activation.     

Characterization of an Invertebrate-Type Dopamine Receptor of the American Cockroach,Periplaneta americana

We have isolated a cDNA coding for a putative invertebrate-type dopamine receptor (Peadop2) from P. americana brain by using a PCR-based strategy. The mRNA is present in samples from brain and salivary glands. We analyzed the distribution of the PeaDOP2 receptor protein with specific affinity-purified polyclonal antibodies. On Western blots, PeaDOP2 was detected in protein samples from brain, subesophageal ganglion, thoracic ganglia, and salivary glands. In immunocytochemical experiments, we detected PeaDOP2 in neurons with their somata being located at the anterior edge of the medulla bilaterally innervating the optic lobes and projecting to the ventro-lateral protocerebrum. In order to determine the functional and pharmacological properties of the cloned receptor, we generated a cell line constitutively expressing PeaDOP2. Activation of PeaDOP2-expressing cells with dopamine induced an increase in intracellular cAMP. In contrast, a C-terminally truncated splice variant of this receptor did not exhibit any functional property by itself. The molecular and pharmacological characterization of the first dopamine receptor from P. americana provides the basis for forthcoming studies focusing on the significance of the dopaminergic system in cockroach behavior and physiology.     

Structure‐Based Mechanism of Oleate Hydratase from Elizabethkingia meningoseptica

Hydratases provide access to secondary and tertiary alcohols by regio‐ and/or stereospecifically adding water to carbon‐carbon double bonds. Thereby, hydroxy groups are introduced without the need for costly cofactor recycling, and that makes this approach highly interesting on an industrial scale. Here we present the first crystal structure of a recombinant oleate hydratase originating from Elizabethkingia meningoseptica in the presence of flavin adenine dinucleotide (FAD). A structure‐based mutagenesis study targeting active site residues identified E122 and Y241 as crucial for the activation of a water molecule and for protonation of the double bond, respectively. Moreover, we also observed that two‐electron reduction of FAD results in a sevenfold increase in the substrate hydration rate. We propose the first reaction mechanism for this enzyme class that explains the requirement for the flavin cofactor and the involvement of conserved amino acid residues in this regio‐ and stereoselective hydration.     

Aerobic biodegradation of polyethylene glycols of different molecular weights in wastewater and seawater

In order to distinguish between aerobic biodegradation of synthetic polymers in fresh and seawater, polyethylene glycols (PEGs) were systematically and comparatively investigated in inocula from municipal wastewater and seawater aquarium filters for the first time. The molecular weight (MW) of the PEGs, (HO(CH(2)CH(2)O)(n)H, n=3-1350) as representatives of water-soluble polymers, ranged from 250 to 57,800Da. The biodegradation was observed by removal of dissolved organic carbon and carbon dioxide production by applying standardized ISO and OECD test methods. Specific analyses using liquid chromatography mass spectrometry (LC-MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) were performed. All PEGs selected were completely biodegradable in freshwater media within 65d. PEGs with an MW up to 14,600Da have a similar degradation pathway which is characterized by gradual splitting of C(2)-units off the chain resulting in formation of short-chain PEGs. In artificial seawater media, full biodegradation of PEGs up to 7400Da required more time than in freshwater. PEGs with MW 10,300 and 14,600Da were only partially degraded whereas PEGs with MW 26,600 and 57,800Da were not degraded for a period of 135d. The biodegradation pathway of PEG 250 and PEG 970 in seawater is similar to that for freshwater. For PEGs having an MW from 2000 to 10,300Da, the degradation pathway in seawater differs from the pathway of the shorter PEGs.     

Atomic Friction Investigations on Ordered Superstructures

We review recent friction measurements on ordered superstructures performed by atomic force microscopy. In particular, we consider ultrathin KBr films on NaCl(001) and Cu(001) surfaces, single and bilayer graphene on SiC(0001), and the herringbone reconstruction of Au(111). Atomically resolved friction images of these systems show periodic features spanning across several unit cells. Although the physical mechanisms responsible for the formation of these superstructures are quite different, the experimental results can be interpreted within the same phenomenological framework. A comparison between experiments and modeling shows that, in the cases of KBr films on NaCl(001) and of graphene films, the tip-surface interaction is well described by a potential with the periodicity of the substrate which is modulated or, respectively, superimposed with a potential with the symmetry of the superstructure.     

Neuregelungen in Vorarlberg zu Spielräumen

Ein Ma?nahmenpaket, bestehend aus dem Spielraumgesetz, dem Beschluss von entsprechenden F?rderungsrichtlinien sowie Novellierungen des Baugesetzes und der Kinderspielplatzverordnung und einer überarbeitung der Wohnbaufondsrichtlinie, soll dazu beitragen, dass sich das Bundesland Vorarlberg als besonders kinder- und jugendfreundliche Region etabliert. Hiefür gilt es, ?ffentliche und private Spielpl?tze und Freir?ume bedarfsgerecht zu erhalten, zu sanieren, neu zu errichten und untereinander zu vernetzen.