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361.
362.
New 5,6-dihydro-1,10-phenanthroline derivatives were prepared in high yield via ytterbium(III) triflate-catalyzed alcoholysis of the corresponding epoxide. Enzymatic transesterifications of racemic alkoxy alcohols afforded enantioselective separations with up to 99% ee. The lipase derived from Burkholderia cepacia (PSCI) was the most efficient, with E-values of up to 200. The steric effect of substituents in the 6-position on reaction time and enantioselectivities was assessed. 相似文献
363.
Leader Peptide‐Free In Vitro Reconstitution of Microviridin Biosynthesis Enables Design of Synthetic Protease‐Targeted Libraries
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Emmanuel Reyna‐González Bianca Schmid Dr. Daniel Petras Prof. Dr. Roderich D. Süssmuth Prof. Dr. Elke Dittmann 《Angewandte Chemie (International ed. in English)》2016,55(32):9398-9401
Microviridins are a family of ribosomally synthesized and post‐translationally modified peptides with a highly unusual architecture featuring non‐canonical lactone as well as lactam rings. Individual variants specifically inhibit different types of serine proteases. Here we have established an efficient in vitro reconstitution approach based on two ATP‐grasp ligases that were constitutively activated using covalently attached leader peptides and a GNAT‐type N‐acetyltransferase. The method facilitates the efficient in vitro one‐pot transformation of microviridin core peptides to mature microviridins. The engineering potential of the chemo‐enzymatic technology was demonstrated for two synthetic peptide libraries that were used to screen and optimize microviridin variants targeting the serine proteases trypsin and subtilisin. Successive analysis of intermediates revealed distinct structure–activity relationships for respective target proteases. 相似文献
364.
José Bonet Mikael Lindströ m Elke Wolf 《Proceedings of the American Mathematical Society》2008,136(12):4267-4273
We characterize those weighted composition operators on weighted Banach spaces of holomorphic functions of type which are an isometry.
365.
We analyze a general class of self-adjoint difference operators , where V
ε is a one-well potential and ε is a small parameter. We construct a Finslerian distance d induced by H
ε and show that short integral curves are geodesics. Then we show that Dirichlet eigenfunctions decay exponentially with a
rate controlled by the Finsler distance to the well. This is analog to semiclassical Agmon estimates for Schr?dinger operators.
Submitted: February 23, 2008. Accepted: May 23, 2008. 相似文献
366.
Siewert I Limberg C Demeshko S Hoppe E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(30):9377-9388
A ligand that offers two parallel malonate binding sites linked by a xanthene backbone, namely, Xanthmal2-, has been utilised to synthesise dinuclear FeII complex [Fe2(Xanthmal)2] (1). The reactivity of 1 in contact with O2 was investigated at -40 degrees C and room temperature. After activation of O2 through interaction with both iron centres the ligand is oxidised: at the Calpha position monooxygenation and peroxide formation occur, partially accompanied by C-C bond cleavage to yield alpha-keto ester groups. To reveal mechanistic details investigations concerning 1) peroxide decomposition, 2) the reactivity of a corresponding mononuclear complex, 3) the influence of monooxygenation of the ligand on the reactivity and 4) product formation in dependence on time were carried out. The results can be explained by postulating formation of high-valent Fe intermediates and ligand-to-metal electron transfer, and the mechanistic scheme derived includes several steps that mimic the (suggested) functioning of non-heme iron enzymes. In agreement with this proposal, ligand oxidation can also be performed catalytically. Furthermore, we show that via a competitive route [(Xanthmal)2Fe2O] (2) is formed, which is unreactive towards O2 and thus is a dead end with respect to ligand oxidation. Both compounds 1 and 2 were fully characterised, and their properties are discussed. 相似文献
367.
Qutaiba Abu‐Salem Cäcilia Maichle‐Mößmer Elke Niquet Norbert Kuhn Prof. Dr. 《无机化学与普通化学杂志》2008,634(14):2463-2465
1,3‐Dimethylcyanuric acid (DMCH) forms on deprotonation and reaction with TlF its thallous salt Tl[DCM] ( 2 ) which is converted to the phosphonium salt [PPh4][DCM] ( 3 ). On the reaction with M(CO)6, the pentacarbonylmetalate salts [Ph4P][(DMC)M(CO)5], M = Cr ( 4a ), Mo ( 4b ) and W ( 4c ) are obtained. IR and NMR data of 4 reveal the DMC anion ( 1 ) to have coordination properties similar to those of pyridine. The crystal structures of 4a and 4c are reported. 相似文献
368.
We have applied an electrophoresis-assisted open-tubular LC-MS method for analyzing intact lipopolysaccharides (LPSs) from Haemophilus influenzae strain RM118 (Rd). We were able to obtain structural information on both core oligosaccharides (OSs) and the lipid A moiety including the sialylation, glycylation, and the distribution of fatty acid residues on the disaccharide backbone of lipid A. The fragmentation patterns of sodiated and protonated LPS molecules were investigated for determining the location of sialic acid. It was found that the tandem mass spectra of sodiated ions provided unambiguous evidence of both sialylated lactose and sialylated lacto-N-neotetraose. In contrast, the fragment ions of protonated ions only offered the evidence for the existence of sialylated lacto-N-neotetraose. The lipid A of Gram-negative bacteria, as the principal endotoxic component of LPS, plays a major role in the pathogenesis of bacterial infections. We have previously characterized lipid A species after mild acid hydrolysis of LPS during which lipid A precipitates. In this study, intact LPS was directly introduced to a tandem mass spectrometer. In-source dissociation strategy was employed, followed by multiple-stage MS/MS on the ions originating from the lipid part to obtain structural information. This is the first time that the structure of lipid A of H. influenzae was characterized by MS/MS on intact LPS molecules without any prior chemical modifications. In the same way information on the OS can be obtained by MS/MS by focusing on ions originating from core OS. 相似文献
369.
Elke Jaime Matthias Westerhausen James Weston 《Journal of organometallic chemistry》2008,693(6):1027-1037
Bis(2-pyridylmethyl)amine 7 reacts with selected dialkylzinc compounds to give dimeric alkylzinc bis(2-pyridylmethyl)amides 8. Regardless of the steric bulk of the alkyl substituent, dimers with central Zn2N2 rings are formed. Compounds 8 undergo spontaneous hydrolysis reactions upon exposure to air/moisture which can be partially controlled if the alkyl substituent R is bulky enough [R = CH(SiMe3)2]. A dimeric compound 9 containing both zinc-alkyl substituents and a μ-OH functionality results. In the course of this reaction, an amide instead of the expected RH is eliminated. Extensive DFT calculations show that the facile formation of a three-centered Zn[μ-(HO?H?NHR)]Zn functionality is a crucial step. Further evidence for the importance of Zn[μ-(X?H?Y)]Zn intermediates (X, Y = O and now N) in the general mechanism of hydrolysis catalyzed by binuclear zinc compounds is thus provided. 相似文献
370.
Investigating morphological changes in treated vs. untreated stone building materials by x-ray micro-CT 总被引:1,自引:0,他引:1
Bugani S Camaiti M Morselli L Van de Casteele E Janssens K 《Analytical and bioanalytical chemistry》2008,391(4):1343-1350
Calcareous stones have been largely used to build historical buildings. Among these, the calcarenites are usually characterized
by a high content of calcite and a high open porosity, which make them very sensitive to the weathering caused by physical
and chemical agents. In order to prevent their deterioration and to retard their decay, different protective products—mainly
polymers—are applied on the stone artefact surfaces. In this work we apply the methodology tested in a preliminary study to
investigate the morphological changes of the internal structure of a biocalcarenite (Lecce stone) by micro x-ray computed
tomography (μ-CT). The porosity and other morphological parameters of the rock before and after the conservation treatment
were calculated on a significant number of samples. The Student’s t test was applied for statistical comparison. The results reveal that the treatment with Paraloid B72 (PB 72) is homogenously
distributed and causes small changes to the natural properties of the rock, whereas the application of a fluoroelastomer (NH)
causes an appreciable decrease in porosity and variation in terms of wall thickness distribution, probably resulting from
its inhomogeneous distribution.
Figure Porosity and other morphological parameters of Lecce stone were investigated by μ-CT: the effect of conservation treatment
with fluoroelastomer on wall thickness distribution is illustrated 相似文献