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41.
42.
M. Sc. Durga Prasad Hari Prof. Dr. Burkhard König 《Angewandte Chemie (International ed. in English)》2013,52(18):4734-4743
The use of diazonium salts for aryl radical generation and C? H arylation processes has been known since 1896 when Pschorr first used the reaction for intramolecular cyclizations. Meerwein developed it further in the early 1900s into a general arylation method. However, this reaction could not compete with the transition‐metal‐mediated formation of C(sp2)? C(sp2) bonds. The replacement of the copper catalyst with iron and titanium compounds improved the situation, but the use of photocatalysis to induce the one‐electron reduction and activation of the diazonium salts is even more advantageous. The first photocatalyzed Pschorr cyclization was published in 1984, and just last year a series of papers described applications of photocatalytic Meerwein arylations leading to aryl–alkene coupling products. In this Minireview we summarize the origins of this reaction and its scope and applications. 相似文献
43.
Camelia Henríquez Burkhard Horstkotte Petr Solich Víctor Cerdà 《Analytical and bioanalytical chemistry》2013,405(21):6761-6769
A fully automated method for the determination of chromate is described. It is based on the selective reaction of Cr(VI) with diphenylcarbazide in acidic media to form a colored complex of Cr(III) with the oxidation product diphenylcarbazone. The reaction was performed within the syringe of an automatic burette containing a magnetic stirrer for homogenization of the sample and the required reagents. In-syringe stirring was made possible using a specially designed driving device placed around the syringe barrel to achieve a rotating magnetic field in the syringe, forcing the stirrer to spin. In a second step, the reaction mixture in the syringe was neutralized to allow in-syringe magnetic-stirring-assisted dispersive liquid–liquid microextraction of the complex into 125 μL of n-hexanol. After phase separation by droplet flotation over 30 s, the organic phase was propelled into a coupled spectrophotometric detection cell. The entire multistep procedure including in-system standard preparation was done within 270 s. The method was used for the analysis of natural waters, achieving average analyte recovery of 103 %, a limit of detection of 0.26 μg L-1, and a repeatability of less than 4 % relative standard deviation. 相似文献
44.
Pure bromopropadiene, BrCH=C=CH2 has been obtained by isomerisation of propargyl bromide in the presence of catalytic amounts of triphenylphosphine. 相似文献
45.
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
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47.
Dr. Andrea Hornemann Dr. Diane M. Eichert Arne Hoehl Dr. Brigitte Tiersch Prof. Gerhard Ulm Prof. Maxim G. Ryadnov Dr. Burkhard Beckhoff 《Chemphyschem》2022,23(4):e202100815
Synchrotron radiation-based Fourier transform infrared spectroscopy enables access to vibrational information from mid over far infrared to even terahertz domains. This information may prove critical for the elucidation of fundamental bio-molecular phenomena including folding-mediated innate host defence mechanisms. Antimicrobial peptides (AMPs) represent one of such phenomena. These are major effector molecules of the innate immune system, which favour attack on microbial membranes. AMPs recognise and bind to the membranes whereupon they assemble into pores or channels destabilising the membranes leading to cell death. However, specific molecular interactions responsible for antimicrobial activities have yet to be fully understood. Herein we probe such interactions by assessing molecular specific variations in the near-THz 400–40 cm−1 range for defined helical AMP templates in reconstituted phospholipid membranes. In particular, we show that a temperature-dependent spectroscopic analysis, supported by 2D correlative tools, provides direct evidence for the membrane-induced and folding-mediated activity of AMPs. The far-FTIR study offers a direct and information-rich probe of membrane-related antimicrobial interactions. 相似文献
48.
Three types of experiments for measuring (n)J(CH) heteronuclear long-range coupling constants are examined and extended with state-of-the-art pulse sequence building-blocks: The use of a HMBC with corresponding reference-HSQC for accurate coupling determination is combined with the constant time technique and the conversion of antiphase magnetization into ZQ/DQ-coherences; CPMG-based LR-CAHSQC and BIRD(r,X)-HSQMBC experiments are examined in detail with respect to their coherence transfer properties; finally, the HSQC-TOCSY-IPAP experiment is introduced, a sequence derived from previously published alpha and beta selective HSQC-TOCSYs using a different spin state selection technique and a recently developed ZQ-suppression method. The experiments are characterized with their advantages and disadvantages and compared using strychnine and menthol as standard molecules. 相似文献
49.
M.Sc. Johannes E. M. N. Klein Dr. Burkhard Miehlich Dr. Michael S. Holzwarth Prof. Dr. Matthias Bauer Dipl.‐Chem. Magdalena Milek Dr. Marat M. Khusniyarov Dr. Gerald Knizia Prof. Dr. Hans‐Joachim Werner Prof. Dr. Bernd Plietker 《Angewandte Chemie (International ed. in English)》2014,53(7):1790-1794
During the past 10 years iron‐catalyzed reactions have become established in the field of organic synthesis. For example, the complex anion [Fe(CO)3(NO)]?, which was originally described by Hogsed and Hieber, shows catalytic activity in various organic reactions. This anion is commonly regarded as being isoelectronic with [Fe(CO)4]2?, which, however, shows poor catalytic activity. The spectroscopic and quantum chemical investigations presented herein reveal that the complex ferrate [Fe(CO)3(NO)]? cannot be regarded as a Fe?II species, but rather is predominantly a Fe0 species, in which the metal is covalently bonded to NO? by two π‐bonds. A metal–N σ‐bond is not observed. 相似文献
50.