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991.
A series of novel muti‐substituted pyrido[4,3‐d]pyrimidin‐4‐one derivatives 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j , 5k , 5l were designed and synthesized by the muti‐step reaction. N,S‐acetal 1 reacted with acetyl acetamide in the presence of zinc nitrate to obtain muti‐substituted pyridine 2 , which reacted with triethyl orthoformate to give 8‐cyano‐5‐methyl‐7‐methylthio‐pyrido[4,3‐d]pyrimidin‐4‐one 3 ; the target compounds 5 were obtained in good yields by the oxidation of 3 with H2O2 in a catalytic amount of sodium tungstate then by the substitution with various substituted phenols. Their structures were confirmed by IR, 1H NMR, EI‐MS, and elemental analyses. The preliminary bioassay indicated that some of them displayed moderate herbicidal activity against dicotyledonous weed Brassica campestris L. at the concentration of 100 mg/L. For example, compounds 5a , 5f , and 5g possessed 76.0%, 62.7%, and 60.2% inhibition against B. campestris at the concentration of 100 mg/L. Moreover, 5a exhibited 58.2% inhibition against B. campestris at the concentration of 10 mg/L.  相似文献   
992.
993.
The presence of micelles from cationic and zwitterionic surfactants increases the apparent acidity of either the keto and the enol forms of 2-phenylacetylfuran (2PAF) and 2-phenylacetylthiophene (2PAT). This effect can be attributed to the affinity of the surfactant micelles for the enolate of the two substrates. Although the equilibrium constants for keto-enol tautomerism of 2PAF and 2PAT, KT=[enol]/[ketone]=pKaKH−pKaEH, do not change much, the presence of micelles provides an efficient method for producing appreciable quantities of the enolates under mild experimental conditions and in aqueous solutions. The obtained rate-profiles for the ketonisation reactions and the consistency of the kinetic rate constants over a wide range of ‘pH’ in several overlapping buffers indicate that the pH of the aqueous pseudophase (but not that at the micellar surface) can be controlled by buffers. Moreover, the increase of the acidity and the decrease of the ‘water’ rate of ketonisation of the enols of 2PAF and 2PAT upon addition of surfactants allow the uncovery of a metal ion catalysed pathway that cannot be observed in absence of surfactants.  相似文献   
994.
Methyltransferases have proven useful to install functional groups site‐specifically in different classes of biomolecules when analogues of their cosubstrate S‐adenosyl‐l ‐methionine (AdoMet) are available. Methyltransferases have been used to address different classes of RNA molecules selectively and site‐specifically, which is indispensable for biophysical and mechanistic studies as well as labeling in the complex cellular environment. However, the AdoMet analogues are not cell‐permeable, thus preventing implementation of this strategy in cells. We present a two‐step enzymatic cascade for site‐specific mRNA modification starting from stable methionine analogues. Our approach combines the enzymatic synthesis of AdoMet with modification of the 5′ cap by a specific RNA methyltransferase in one pot. We demonstrate that a substrate panel including alkene, alkyne, and azido functionalities can be used and further derivatized in different types of click reactions.  相似文献   
995.
Cyanobactins are a rapidly growing family of linear and cyclic peptides produced by cyanobacteria. Kawaguchipeptins A and B, two macrocyclic undecapeptides reported earlier from Microcystis aeruginosa NIES‐88, are shown to be products of the cyanobactin biosynthetic pathway. The 9 kb kawaguchipeptin (kgp) gene cluster was identified in a 5.26 Mb draft genome of Microcystis aeruginosa NIES‐88. We verified that this gene cluster is responsible for the production of the kawaguchipeptins through heterologous expression of the kgp gene cluster in Escherichia coli. The KgpF prenyltransferase was overexpressed and was shown to prenylate C‐3 of Trp residues in both linear and cyclic peptides in vitro. Our findings serve to further enhance the structural diversity of cyanobactins to include tryptophan‐prenylated cyclic peptides.  相似文献   
996.
β-Lactamases are bacterial enzymes conferring resistance to β-lactam antibiotics in clinically-relevant pathogens, and represent relevant drug targets. Recently, the identification of new boronic acids (i.e. RPX7009) paved the way to the clinical application of these molecules as potential drugs. Here, we screened in silico a library of ~1400 boronic acids as potential AmpC β-lactamase inhibitors. Six of the most promising candidates were evaluated in biochemical assays leading to the identification of potent inhibitors of clinically-relevant β-lactamases like AmpC, KPC-2 and CTX-M-15. One of the selected compounds showed nanomolar K i value with the clinically-relevant KPC-2 carbapenemase, while another one exhibited broad spectrum inhibition, being also active on Enterobacter AmpC and the OXA-48 class D carbapenemase.  相似文献   
997.
Electron capture dissociation (ECD) and electron transfer dissociation (ETD) in metal-peptide complexes are dependent on the metal cation in the complex. The divalent transition metals Ni2+, Cu2+, and Zn2+ were used as charge carriers to produce metal-polyhistidine complexes in the absence of remote protons, since these metal cations strongly bind to neutral histidine residues in peptides. In the case of the ECD and ETD of Cu2+-polyhistidine complexes, the metal cation in the complex was reduced and the recombination energy was redistributed throughout the peptide to lead a zwitterionic peptide form having a protonated histidine residue and a deprotonated amide nitrogen. The zwitterion then underwent peptide bond cleavage, producing a and b fragment ions. In contrast, ECD and ETD induced different fragmentation processes in Zn2+-polyhistidine complexes. Although the N–Cα bond in the Zn2+-polyhistidine complex was cleaved by ETD, ECD of Zn2+-polyhistidine induced peptide bond cleavage accompanied with hydrogen atom release. The different fragmentation modes by ECD and ETD originated from the different electronic states of the charge-reduced complexes resulting from these processes. The details of the fragmentation processes were investigated by density functional theory.
Graphical Abstract ?
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998.
Formation of magnetite nanocrystals by magnetotactic bacteria is controlled by specific proteins which regulate the particles’ nucleation and growth. One such protein is Mms6. This small, amphiphilic protein can self‐assemble and bind ferric ions to aid in magnetite formation. To understand the role of Mms6 during in vitro iron oxide precipitation we have performed in situ pH titrations. We find Mms6 has little effect during ferric salt precipitation, but exerts greatest influence during the incorporation of ferrous ions and conversion of this salt to mixed‐valence iron minerals, suggesting Mms6 has a hitherto unrecorded ferrous iron interacting property which promotes the formation of magnetite in ferrous‐rich solutions. We show ferrous binding to the DEEVE motif within the C‐terminal region of Mms6 by NMR spectroscopy, and model these binding events using molecular simulations. We conclude that Mms6 functions as a magnetite nucleating protein under conditions where ferrous ions predominate.  相似文献   
999.
In a previous study, the iodate-sulfite proton autoactivated reaction (Landolt reaction) was shown to exhibit spatial bistability and spatiotemporal oscillations when operated in an open spatial reactor with fixed "thickness", i.e., feed boundary to core distance. Here, we show that the spatial reactors with conical geometry enable one to rapidly probe the sensitivity of the above phenomena over a large range of the "thickness" parameter. This often-neglected parameter in chemical pattern studies plays an important role on the selection and stability of states. We reveal that the quenching capacity of slow diffusing polyacrylate ions on the spatiotemporal oscillations depends on this "thickness". The presented results should be useful for further research on reaction diffusion patterns and chemomechanical structures.  相似文献   
1000.
Silica-based inorganic–organic hybrid thin films embedding the organically modified oxohafnium clusters (Hf4O2(OMc)12, OMc=OC(O)–C(CH3)=CH2) were obtained by photo-activated free radical copolymerisation of the methacrylate groups of the cluster with those of the pre-hydrolysed (methacryloxypropyl)trimethoxysilane (MAPTMS, (CH2=C(CH3)C(O)O)(CH2)3Si(OCH3)3). By this route, a covalent anchoring of the cluster to the forming silica network was achieved. Samples characterized by two different Si/Hf compositions (18:1, 5:1) were prepared. The surface and in-depth composition of the thin films were investigated through Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). XPS depth profiles performed on the thin layers evidenced a homogenous in depth distribution of the hafnium guest species within the whole silica films and sharp film-substrate interfaces. Broad band dielectric spectroscopy (BDS) measurements permitted to investigate the electric response of the obtained films in the frequency and temperature range of 40 Hz – 1 MHz and 0–160°C.  相似文献   
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