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131.
Siitonen V Claesson M Patrikainen P Aromaa M Mäntsälä P Schneider G Metsä-Ketelä M 《Chembiochem : a European journal of chemical biology》2012,13(1):120-128
Nogalamycin is an anthracycline antibiotic that has been shown to exhibit significant cytotoxicity. Its biological activity requires two deoxysugar moieties: nogalose and nogalamine, which are attached at C7 and C1, respectively, of the aromatic polyketide aglycone. Curiously, the aminosugar nogalamine is also connected through a C-C bond between C2 and C5'. Despite extensive molecular genetic characterization of early biosynthetic steps, nogalamycin glycosylation has not been investigated in detail. Here we show that expression of the majority of the gene cluster in Streptomyces albus led to accumulation of three new anthracyclines, which unexpectedly included nogalamycin derivatives in which nogalamine was replaced either by rhodosamine with the C-C bond intact (nogalamycin R) or by 2-deoxyfucose without the C-C bond (nogalamycin F). In addition, a monoglycosylated intermediate-3',4'-demethoxynogalose-1-hydroxynogalamycinone-was isolated. Importantly, when the remaining biosynthetic genes were introduced into the heterologous host by using a two-plasmid system, nogalamycin could be isolated from the cultures, thus indicating that the whole gene cluster had been identified. We further show that one of the three glycosyltransferases (GTs) residing in the cluster-snogZ-appears to be redundant, whereas gene inactivation experiments revealed that snogE and snogD act as nogalose and nogalamine transferases, respectively. The substrate specificity of the nogalamine transferase SnogD was demonstrated in vitro: the enzyme was able to remove 2deoxyfucose from nogalamycin F. All of the new compounds were found to inhibit human topoisomerase I in activity measurements, whereas only nogalamycin R showed minor activity against topoisomerase II. 相似文献
132.
The development of innovative metal catalysis for selective bond formation is an important task in organic chemistry. The group 13 metal indium is appealing for catalysis because indium-based reagents are minimally toxic, selective, and tolerant toward various functional groups. Among elements in this group, the most stable oxidation state is typically +3, but in molecules with larger group 13 atoms, the chemistry of the +1 oxidation state is also important. The use of indium(III) compounds in organic synthesis has been well-established as Lewis acid catalysts including asymmetric versions thereof. In contrast, only sporadic examples of the use of indium(I) as a stoichiometric reagent have been reported: to the best of our knowledge, our investigations represent the first synthetic method that uses a catalytic amount of indium(I). Depending on the nature of the ligand or the counteranion to which it is coordinated, indium(I) can act as both a Lewis acid and a Lewis base because it has both vacant p orbitals and a lone pair of electrons. This potential ambiphilicity may offer unique reactivity and unusual selectivity in synthesis and may have significant implications for catalysis, particularly for dual catalytic processes. We envisioned that indium(I) could be employed as a metallic Lewis base catalyst to activate Lewis acidic boron-based pronucleophiles for selective bond formation with suitable electrophiles. Alternatively, indium(I) could serve as an ambiphilic catalyst that activates both reagents at a single center. In this Account, we describe the development of low-oxidation state indium catalysts for carbon-carbon bond formation between boron-based pronucleophiles and various electrophiles. We discovered that indium(I) iodide was an excellent catalyst for α-selective allylations of C(sp(2)) electrophiles such as ketones and hydrazones. Using a combination of this low-oxidation state indium compound and a chiral semicorrin ligand, we developed catalytic highly enantioselective allylation, crotylation, and α-chloroallylation reactions of hydrazones. These transformations proceeded with rare constitutional selectivities and remarkable diastereoselectivities. Furthermore, indium(I) triflate served as the most effective catalyst for allylations and propargylations of C(sp(3)) electrophiles such as O,O-acetals, N,O-aminals, and ethers, and we applied this methodology to carbohydrate chemistry. In addition, a catalyst system composed of indium(I) chloride and a chiral silver BINOL-phosphate facilitated the highly enantioselective allylation and allenylation of N,O-aminals. Overall, these discoveries demonstrate the versatility, efficiency, and sensitivity of low-oxidation state indium catalysts in organic synthesis. 相似文献
133.
Leonhard M. Kick Dr. Sabrina Harteis Dr. Maximilian F. Koch Dr. Sabine Schneider 《Chembiochem : a European journal of chemical biology》2017,18(22):2242-2246
Inteins carry out protein-splicing reactions, which are used in protein chemistry, protein engineering and biotechnological applications. Rearrangement of the order of the domains in split-inteins results in head-to-tail cyclisation of the target sequence, which can be used for genetic encoding and expression of libraries of cyclic peptides (CPs). The efficiency of the splicing reaction depends on the target sequence. Here we used mass spectrometry to assess in vivo cyclic peptide formation from different hexameric target sequences by the DnaE split-inteins from Synechocystis sp. and Nostoc punctiforme, revealing a strong impact of the target sequence and of the intein on the intracellular peptide concentration. Furthermore, we determined the crystal structures of their pre-splicing complexes, which allowed us to identify F-block Asp17 as crucial for the DnaE-mediated splicing reaction. 相似文献
134.
Janine Will Lars Schneider Dr. Jonathan Becker Jun.-Prof. Dr. Sabine Becker Andreas Miska Christopher Gawlig Prof. Dr. Siegfried Schindler 《Israel journal of chemistry》2020,60(10-11):999-1003
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. 相似文献
135.
Clio Azina Tim Bartsch Damian M. Holzapfel Martin Dahlqvist Johanna Rosen Lukas Löfler Alba San Jose Mendez Marcus Hans Daniel Primetzhofer Jochen M. Schneider 《Journal of the American Ceramic Society》2023,106(4):2652-2665
Herein we report on the synthesis of a metastable (Cr,Y)2AlC MAX phase solid solution by co-sputtering from a composite Cr–Al–C and elemental Y target, at room temperature, followed by annealing. However, direct high-temperature synthesis resulted in multiphase films, as evidenced by X-ray diffraction analyses, room-temperature depositions, followed by annealing to 760°C led to the formation of phase pure (Cr,Y)2AlC by diffusion. Higher annealing temperatures caused a decomposition of the metastable phase into Cr2AlC, Y5Al3, and Cr-carbides. In contrast to pure Cr2AlC, the Y-containing phase crystallizes directly in the MAX phase structure instead of first forming a disordered solid solution. Furthermore, the crystallization temperature was shown to be Y-content dependent and was increased by ∼200°C for 5 at.% Y compared to Cr2AlC. Calculations predicting the metastable phase formation of (Cr,Y)2AlC and its decomposition are in excellent agreement with the experimental findings. 相似文献
136.
Mohammad Ahmadi Dr. Yaghoub Ahmadyousefi Zahra Salimi Dr. Rasoul Mirzaei Dr. Rezvan Najafi Dr. Bagher Amirheidari Dr. Fatemeh Rahbarizadeh Javad Kheshti Armin Safari Dr. Meysam Soleimani 《ChemMedChem》2023,18(3):e202200506
Active targeting using biological ligands has emerged as a novel strategy for the targeted delivery of diagnostic agents to tumor cells. Conjugating functional targeting moieties with diagnostic probes can increase their accumulation in tumor cells and tissues, enhancing signal detection and, thus, the sensitivity of diagnosis. Due to their small size, ease of chemical synthesis and site-specific modification, high tissue penetration, low immunogenicity, rapid blood clearance, low cost, and biosafety, peptides offer several advantages over antibodies and proteins in diagnostic applications. Epidermal growth factor receptor (EGFR) is one of the most promising cancer biomarkers for actively targeting diagnostic and therapeutic agents to tumor cells due to its active involvement and overexpression in various cancers. Several peptides for EGFR-targeting have been identified in the last decades, which have been obtained by multiple means including derivation from natural proteins, phage display screening, positional scanning synthetic combinatorial library, and in silico screening. Many studies have used these peptides as a targeting moiety for diagnosing different cancers in vitro, in vivo, and in clinical trials. This review summarizes the progress of EGFR-targeting peptide-based assays in the molecular diagnosis of cancer. 相似文献
137.
Laura Neuendorf Zakariae Hammal Prof. Dr. Armin Fricke Prof. Dr.-Ing. Norbert Kockmann 《化学,工程师,技术》2023,95(7):1134-1145
Solvent extraction as environmental benign separation technique can be modeled in physical detail by population balance of the droplet size distribution. However, much information on the droplet generation and coalescence is necessary for representative results. In this contribution, we present a comparison of AI-evaluated experimental and simulated data on the behavior of a stirred solvent extraction column with an inner diameter of 32 mm. Lab experiments were performed using the standard test system with n-butyl acetate, acetone, and deionized water. A digital camera is placed in front of the middle section as well as the head of the column. Droplet size evaluation is performed using a retrained neural net (Mask R-CNN). The stirred DN32 extraction column is modeled and simulated using a 1D CFD population balance software. The simulation allows for behavior analysis, trends comparison, and validation of the hydrodynamics and mass transfer performances. 相似文献
138.
Sara Fateixa Marc Landauer Johannes Schneider Shanmugam Kumar Robert Böhm 《大分子材料与工程》2023,308(8):2300060
Novel low-cost materials to uptake and detect vestigial amounts of pesticides are highly desirable for water quality monitoring. Herein, are demonstrated, for the first time, surface-enhanced Raman scattering (SERS) sensors enabled via additively manufactured lattices coated with plasmonic nanoparticles (NPs) for detecting pesticides in real water samples. The architected lattices comprising polypropylene (PP) and multiwall carbon nanotubes (MWCNTs) are realized via fused filament fabrication (FFF). In the first stage, the SERS performance of the PP/MWCNT filaments coated with distinct metallic NPs (Ag NPs and Au NPs) is evaluated using methylene blue (MB) as molecular probe. Thereafter, distinctly architected hybrid SERS sensors with periodic porous and fully dense geometries are investigated as adsorbents to uptake MB from aqueous solutions and subsequent detection using SERS. The spatial distribution of MB and Ag NPs on the FFF-printed lattices is accomplished by SERS imaging. The best hybrid composite is used as SERS probing system to detect low amounts of pesticides (thiram and paraquat) and offers a detection limit of 100 nm for both pesticides. As a proof-of-concept, FFF-enabled test strips are used to detect in loco paraquat molecules spiked on real water samples (Estuary Aveiro water and tap water) using a portable Raman spectrometer. 相似文献
139.
Interaction between water vapor and Nafion™ perfluorosulfonate ionomer has been investigated via combined flow microcalorimetry and isothermal sorption over a wide range of water relative pressure. The molar enthalpy of sorption was determined for the untreated polymer, the residual polymer after extraction by aqueous propanol, and the extracted fraction. The extract appears to be low molecular weight Nafion™ but with an equivalent weight more than double that of the unextracted polymer. The equivalent weight of the residual polymer is slightly lower than that of the original Nafion™, apparently due to partial alkylation. Molar enthalpy for formation of the sulfonic acid monohydrate is about the same for the residual and unextracted polymers, but much greater for the extracted fraction. For untreated Nafion™, the magnitude and concentration dependence of the molar enthalpy indicates that sorption of water exhibits a clear progression from hydronium ion formation (≤1 H2O/SO3H) through growth of isolated hydrated clusters (≤6 H2O/SO3H) to a continuous internal water phase. A more complicated process occurs for the extract and residual polymer fractions in that an endotherm associated with elastic compression of the polymer matrix surrounding isolated water clusters is superimposed on the hydration exotherm over the concentration range of cluster growth. There is only a minor indication of this endotherm for unextracted Nafion™ because of more facile relaxation of the polymer structure due to plasticization by the low molecular weight fraction. 相似文献
140.
Matthias Berger Kurt Laumen Manfred P. Schneider 《Journal of the American Oil Chemists' Society》1992,69(10):955-960
Regioisomerically pure 1,3-sn-diacylglycerols are conveniently prepared in high yields (>80%) and in large quantities by enzymatic esterification of glycerol
in the presence of various 1,3-selective lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) and a variety of different acyl donors like free fatty acids, fatty acid alkyl esters and vinyl esters. All reactions are
carried out in aprotic organic solvents of low water content, namelyn-hexane, diethyl ether or tBuOMe. The creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol
and the hydrophobic reaction media by the adsorption of glycerol onto a solid support prior to use was essential for the success
of these transformations. The effects of reaction conditions and the regioselectivities of the lipases on the product yields
are described in detail. 相似文献