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71.
Jana Špaková Raschmanová Miroslava Martinková Jozef Gonda Alena Uhríková 《Chemical Papers》2013,67(10):1317-1329
The stereoselective synthesis of sulfamisterin I and its unnatural analogues II and V in their protected form was achieved through a common strategy. The Wittig reaction of aldehydes VIII and IX with the C14 hydrophobic side-chain X served as the key C-C connecting transformation. Subsequent functional group inter-conversions in the coupling products XI and XX completed the total synthesis. 相似文献
72.
Uwe Lindner Jana Lingott Silke Richter Norbert Jakubowski Ulrich Panne 《Analytical and bioanalytical chemistry》2013,405(6):1865-1873
Hydrophilic interaction chromatography (HILIC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was optimized for speciation analysis of gadolinium-based contrast agents in environmental samples, in particular surface river waters and plants. Surface water samples from the Teltow channel, near Berlin, were investigated over a distance of 5 km downstream from the influx of a wastewater treatment plant. The total concentration of gadolinium increased significantly from 50 to 990 ng?L?1 due to the influx of the contrast agents. After complete mixing with the river water, the concentration remained constant over a distance of at least 4 km. Two main substances [Dotarem® (Gd-DOTA) and Gadovist® (Gd-BT-DO3A)] have been identified in the river water using standards. A gadolinium-based contrast agent, possibly Gd-DOTA (Dotarem®), was also detected in water plant samples taken from the Teltow channel. Therefore, uptake of contrast agents [Gadovist® (Gd-BTDO3A), Magnevist® (Gd-DTPA), Omniscan® (Gd-DTPA-BMA), Dotarem® (Gd-DOTA), and Multihance® (Gd-BOPTA)] by plants was investigated in a model experiment using Lepidium sativum (cress plants). HILIC–ICP-MS was used for identification of different contrast agents, and a first approach for quantification using aqueous standard solutions was tested. For speciation analysis, all investigated contrast agents could be extracted from the plant tissues with a recovery of about 54 % for Multihance® (Gd-BOPTA) up to 106 % for Gadovist® (Gd-BT-DO3A). These experiments demonstrate that all contrast agents investigated are transported from the roots to the leaves where the highest content was measured. 相似文献
73.
Erik Andris Rafael Navrtil Juraj Jaík Martin Srnec Mnica Rodríguez Miquel Costas Jana Roithov 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9721-9726
Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group 8. Using mass spectrometry, we prepared and characterized two such complexes: [(N4Py)CoIII(O)]+ ( 1 ) and [(N4Py)CoIV(O)]2+ ( 2 ). Infrared photodissociation spectroscopy revealed that the Co?O bond in 1 is rather strong, in accordance with its lack of chemical reactivity. On the contrary, 2 has a very weak Co?O bond characterized by a stretching frequency of ≤659 cm?1. Accordingly, 2 can abstract hydrogen atoms from non‐activated secondary alkanes. Previously, this reactivity has only been observed in the gas phase for small, coordinatively unsaturated metal complexes. Multireference ab‐initio calculations suggest that 2 , formally a cobalt(IV)‐oxo complex, is best described as cobalt(III)‐oxyl. Our results provide important data on changes to metal‐oxo bonding behind the oxo wall and show that cobalt‐oxo complexes are promising targets for developing highly active C?H oxidation catalysts. 相似文献
74.
Marketa Ryvolova Kristyna Smerkova Jana Chomoucka Jaromir Hubalek Vojtech Adam Rene Kizek 《Electrophoresis》2013,34(6):801-808
Cisplatin, carboplatin, and oxaliplatin represent three generations of platinum based drugs applied successfully for cancer treatment. As a consequence of the employment of platinum based cytostatics in the cancer treatment, it became necessary to study the mechanism of their action. Current accepted opinion is the formation of Pt‐DNA adducts, but the mechanism of their formation is still unclear. Nanomaterials, as a progressively developing branch, can offer a tool for studying the interactions of these drugs with DNA. In this study, fluorescent CdTe quantum dots (QDs, λem = 525 nm) were employed to investigate the interactions of platinum cytostatics (cisplatin, carboplatin, and oxaliplatin) with DNA fragment (500 bp, c = 25 μg/mL). Primarily, the fluorescent behavior of QDs in the presence of platinum cytostatics was monitored and major differences in the interaction of QDs with tested drugs were observed. It was found that the presence of carboplatin (c = 0.25 mg/mL) had no significant influence on QDs fluorescence; however cisplatin and oxaliplatin quenched the fluorescence significantly (average decrease of 20%) at the same concentration. Subsequently, the amount of platinum incorporated in DNA was determined by QDs fluorescence quenching. Best results were reached using oxaliplatin (9.4% quenching). Linear trend (R2 = 0.9811) was observed for DNA platinated by three different concentrations of oxaliplatin (0.250, 0.125, and 0.063 mg/mL). Correlation with differential pulse voltammetric measurements provided linear trend (R2 = 0.9511). As a conclusion, especially in the case of oxaliplatin‐DNA adducts, the quenching was the most significant compared to cisplatin and nonquenching carboplatin. 相似文献
75.
Jitka Daďová Susanne Kümmel Christian Feldmeier Jana Cibulková Dr. Richard Pažout Dr. Jaroslav Maixner Prof. Dr. Ruth M. Gschwind Prof. Dr. Burkhard König Dr. Radek Cibulka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1066-1075
A series of 10‐arylflavins (10‐phenyl‐, 10‐(2′,6′‐dimethylphenyl)‐, 10‐(2′,6′‐diethylphenyl)‐, 10‐(2′,6′‐diisopropylphenyl)‐, 10‐(2′‐tert‐butylphenyl)‐, and 10‐(2′,6′‐dimethylphenyl)‐3‐methylisoalloxazine ( 2 a – f )) was prepared as potentially nonaggregating flavin photocatalysts. The investigation of their structures in the crystalline phase combined with 1H‐DOSY NMR spectroscopic experiments in CD3CN, CD3CN/D2O (1:1), and D2O confirm the decreased ability of 10‐arylflavins 2 to form aggregates relative to tetra‐O‐acetyl riboflavin ( 1 ). 10‐Arylflavins 2 a – d do not interact by π–π interactions, which are restricted by the 10‐phenyl ring oriented perpendicularly to the isoalloxazine skeleton. On the other hand, N3? H???O hydrogen bonds were detected in their crystal structures. In the structure of 10‐aryl‐3‐methylflavin ( 2 f ) with a substituted N3 position, weak C? H???O bonds and weak π–π interactions were found. 10‐Arylflavins 2 were tested as photoredox catalysts for the aerial oxidation of 4‐methoxybenzyl alcohol to the corresponding aldehyde (model reaction), thus showing higher efficiency relative to 1 . The quantum yields of 4‐methoxybenzyl alcohol oxidation reactions mediated by arylflavins 2 were higher by almost one order of magnitude relative to values in the presence of 1 . 相似文献
76.
A new method of HPLC column retentivity testing utilizes polymeric probes instead of conventional sets of low molar mass substances. The procedure allows at least semiquantitative, separate and independent evaluation of adsorption and partition properties of column packings. In this present work, the method is applied for comparison of the polar interactivities of selected silica gel C18 HPLC columns. It is shown that free silanols which remained on the surface of the end-capped silica C18 column packings are accessible for interaction with highly polar macromolecules. High molar mass polymeric test probes are adsorbed on the surface silanols and their retention volumes increase. As result, deviations from regular size-exclusion chromatographic (SEC) behavior are observed. The extent of retention volume changes depends on both the nature of polymer probes and on column packing type. Adsorption of macromolecules can be suppressed by addition of a highly polar substance to the mobile phase. The amount of polar additive which is needed to attain regular SEC elution of the polymer probe depends on the column packing type and can be used as a characteristic of silanophilic column interactivity. Courses of dependences of retention volumes on sizes of macromolecules indicate the presence of "U-turn" adsorption which allows two and more silanols situated among C18 groups to be occupied simultaneously with the same macromolecule. 相似文献
77.
Daniel Moser Dr. Kalipada Jana Prof. Dr. Christof Sparr 《Angewandte Chemie (International ed. in English)》2023,62(39):e202309053
Herein, we describe the feasibility of atroposelective PIII/PV=O redox organocatalysis by the Staudinger–aza-Wittig reaction. The formation of isoquinoline heterocycles thereby enables the synthesis of a broad range of valuable atropisomers under mild conditions with enantioselectivities of up to 98 : 2 e.r. Readily prepared azido cinnamate substrates convert in high yield with stereocontrol by a chiral phosphine catalyst, which is regenerated using a silane reductant under Brønsted acid co-catalysis. The reaction provides access to diversified aryl isoquinolines, as well as benzoisoquinoline and naphthyridine atropisomers. The products are expeditiously transformed into N-oxides, naphthol and triaryl phosphine variants of prevalent catalysts and ligands. With dinitrogen release and aromatization as ideal driving forces, it is anticipated that atroposelective redox organocatalysis provides access to a multitude of aromatic heterocycles with precise control over their configuration. 相似文献
78.
Dr. Manju P. Maman Dr. Tamilselvi Gurusamy Dr. Arun K. Pal Dr. Rajkumar Jana Dr. Kothandaraman Ramanujam Dr. Ayan Datta Dr. Sukhendu Mandal 《Angewandte Chemie (International ed. in English)》2023,62(27):e202305462
The fixing of N2 to NH3 is challenging due to the inertness of the N≡N bond. Commercially, ammonia production depends on the energy-consuming Haber-Bosch (H−B) process, which emits CO2 while using fossil fuels as the sources of hydrogen and energy. An alternative method for NH3 production is the electrochemical nitrogen reduction reaction (NRR) process as it is powered by renewable energy sources. Here, we report a tiara-like nickel-thiolate cluster, [Ni6(PET)12] (where, PET=2-phenylethanethiol)] as an efficient electro-catalyst for the electrochemical NRR at ambient conditions. Ammonia (NH3: 16.2±0.8 μg h−1 cm−2) was the only nitrogenous product over the potential of −2.3 V vs. Fc+/Fc with a Faradaic efficiency of 25%±1.7. Based on theoretical calculations, NRR by [Ni6(PET)12] proceeds through both the distal and alternating pathways with an onset potential of −1.84 V vs. RHE (i.e., −2.46 V vs. Fc+/Fc) which corroborates with the experimental findings. 相似文献
79.
Dr. Jianing Xie Dr. Axel Pahl Dr. Adrian Krzyzanowski Anna Krupp Dr. Jie Liu Sandra Koska Beate Schölermann Dr. Ruirui Zhang Jana Bonowski Dr. Sonja Sievers Prof. Dr. Carsten Strohmann Dr. Slava Ziegler Dr. Michael Grigalunas Prof. Dr. Herbert Waldmann 《Angewandte Chemie (International ed. in English)》2023,62(48):e202310222
Monoterpene indole alkaloids (MIAs) are endowed with high structural and spatial complexity and characterized by diverse biological activities. Given this complexity-activity combination in MIAs, rapid and efficient access to chemical matter related to and with complexity similar to these alkaloids would be highly desirable, since such compound classes might display novel bioactivity. We describe the design and synthesis of a pseudo-natural product (pseudo-NP) collection obtained by the unprecedented combination of MIA fragments through complexity-generating transformations, resulting in arrangements not currently accessible by biosynthetic pathways. Cheminformatic analyses revealed that both the pseudo-NPs and the MIAs reside in a unique and common area of chemical space with high spatial complexity-density that is only sparsely populated by other natural products and drugs. Investigation of bioactivity guided by morphological profiling identified pseudo-NPs that inhibit DNA synthesis and modulate tubulin. These results demonstrate that the pseudo-NP collection occupies similar biologically relevant chemical space that Nature has endowed MIAs with. 相似文献
80.
Dr. Samuel M. Meier M. Sc. Dominique Kreutz Dr. Lilli Winter M. Sc. Matthias H. M. Klose M. Sc. Klaudia Cseh M. Sc. Tamara Weiss Dr. Andrea Bileck M. Sc. Beatrix Alte Dr. Johanna C. Mader M. Sc. Samir Jana Dr. Annesha Chatterjee Dr. Arindam Bhattacharyya Michaela Hejl Dr. Michael A. Jakupec Priv.-Doz. Dr. Petra Heffeter Prof. Dr. Walter Berger Prof. Dr. Christian G. Hartinger Prof. Dr. Bernhard K. Keppler Prof. Dr. Gerhard Wiche Prof. Dr. Christopher Gerner 《Angewandte Chemie (International ed. in English)》2017,56(28):8267-8271
Organometallic metal(arene) anticancer agents require ligand exchange for their anticancer activity and this is generally believed to confer low selectivity for potential cellular targets. However, using an integrated proteomics-based target-response profiling approach as a potent hypothesis-generating procedure, we found an unexpected target selectivity of a ruthenium(arene) pyridinecarbothioamide (plecstatin) for plectin, a scaffold protein and cytolinker, which was validated in a plectin knock-out model in vitro. Plectin targeting shows potential as a strategy to inhibit tumor invasiveness as shown in cultured tumor spheroids while oral administration of plecstatin-1 to mice reduces tumor growth more efficiently in the invasive B16 melanoma than in the CT26 colon tumor model. 相似文献