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71.
Biocatalytic Synthesis of Nitriles through Dehydration of Aldoximes: The Substrate Scope of Aldoxime Dehydratases 下载免费PDF全文
Tobias Betke Jun Higuchi Philipp Rommelmann Keiko Oike Dr. Taiji Nomura Prof.Dr. Yasuo Kato Prof.Dr. Yasuhisa Asano Prof.Dr. Harald Gröger 《Chembiochem : a European journal of chemical biology》2018,19(8):768-779
Nitriles, which are mostly needed and produced by the chemical industry, play a major role in various industry segments, ranging from high‐volume, low‐price sectors, such as polymers, to low‐volume, high‐price sectors, such as chiral pharma drugs. A common industrial technology for nitrile production is ammoxidation as a gas‐phase reaction at high temperature. Further popular approaches are substitution or addition reactions with hydrogen cyanide or derivatives thereof. A major drawback, however, is the very high toxicity of cyanide. Recently, as a synthetic alternative, a novel enzymatic approach towards nitriles has been developed with aldoxime dehydratases, which are capable of converting an aldoxime in one step through dehydration into nitriles. Because the aldoxime substrates are easily accessible, this route is of high interest for synthetic purposes. However, whenever a novel method is developed for organic synthesis, it raises the question of substrate scope as one of the key criteria for application as a “synthetic platform technology”. Thus, the scope of this review is to give an overview of the current state of the substrate scope of this enzymatic method for synthesizing nitriles with aldoxime dehydratases. As a recently emerging enzyme class, a range of substrates has already been studied so far, comprising nonchiral and chiral aldoximes. This enzyme class of aldoxime dehydratases shows a broad substrate tolerance and accepts aliphatic and aromatic aldoximes, as well as arylaliphatic aldoximes. Furthermore, aldoximes with a stereogenic center are also recognized and high enantioselectivities are found for 2‐arylpropylaldoximes, in particular. It is further noteworthy that the enantiopreference depends on the E and Z isomers. Thus, opposite enantiomers are accessible from the same racemic aldehyde and the same enzyme. 相似文献
72.
Tobias Schröder Satya Narayan Sahu Dario Anselmetti Jochen Mattay 《Israel journal of chemistry》2011,51(7):725-742
Self-assembly by H-bonding and by metal-coordination of functionalized calix[4]arenes and cavitands to large supramolecular capsules is described. In addition, a new method of analyzing supramolecular recognition processes at the single molecule level is discussed. By measuring interaction forces in a hydrogen-bonded assembly using single-molecule force spectroscopy (SMFS), the dynamics of the self-assembly process can be evaluated. In the future, consequent application of this new technique will influence supramolecular design principles and the use of non-covalent interactions as construction elements in the field of nanotechnology. 相似文献
73.
Anna Sib Tobias M. Milzarek Alexander Herrmann Dr. Lila Oubraham Jonas I. Müller Prof. Dr. Andreas Pichlmair Prof. Dr. Ruth Brack-Werner Prof. Dr. Tobias A. M. Gulder 《Chembiochem : a European journal of chemical biology》2020,21(4):492-495
Sorbicillinoids are fungal polyketides characterized by highly complex and diverse molecular structures, with considerable stereochemical intricacy combined with a high degree of oxygenation. Many sorbicillinoids possess promising biological activities. An interesting member of this natural product family is sorbicatechol A, which is reported to have antiviral activity, particularly against influenza A virus (H1N1). Through a straightforward, one-pot chemoenzymatic approach with recently developed oxidoreductase SorbC, the characteristic bicyclo[2.2.2]octane core of sorbicatechol is structurally diversified by variation of its natural 2-methoxyphenol substituent. This facilitates the preparation of a focused library of structural analogues bearing substituted aromatic systems, alkanes, heterocycles, and ethers. Fast access to this structural diversity provides an opportunity to explore the antiviral potential of the sorbicatechol family. 相似文献
74.
Two‐Step Protein Labeling by Using Lipoic Acid Ligase with Norbornene Substrates and Subsequent Inverse‐Electron Demand Diels–Alder Reaction 下载免费PDF全文
Marcel Best Anna Degen Mathis Baalmann Tobias T. Schmidt Dr. Richard Wombacher 《Chembiochem : a European journal of chemical biology》2015,16(8):1158-1162
Inverse‐electron‐demand Diels–Alder cycloaddition (DAinv) between strained alkenes and tetrazines is a highly bio‐orthogonal reaction that has been applied in the specific labeling of biomolecules. In this work we present a two‐step labeling protocol for the site‐specific labeling of proteins based on attachment of a highly stable norbornene derivative to a specific peptide sequence by using a mutant of the enzyme lipoic acid ligase A (LplAW37V), followed by the covalent attachment of tetrazine‐modified fluorophores to the norbornene moiety through the bio‐orthogonal DAinv . We investigated 15 different norbornene derivatives for their selective enzymatic attachment to a 13‐residue lipoic acid acceptor peptide (LAP) by using a standardized HPLC protocol. Finally, we used this two‐step labeling strategy to label proteins in cell lysates in a site‐specific manner and performed cell‐surface labeling on living cells. 相似文献
75.
Processing behavior and mechanical properties of autopolymerizing hypoallergenic denture base polymers 下载免费PDF全文
Driven by the phenomenon of increasing irritations and allergic reactions of dental prosthesis carriers preferably due to residual methyl methacrylate monomer in conventional dental materials, autopolymerizing hypoallergenic denture base polymers were prepared as two‐component materials in the shape of paste/paste‐ or powder/liquid systems. The processing behavior of these materials was investigated regarding the processing and solidification times also in dependence on the polymerization catalyst concentration, whereas the whole processing and curing characteristics and the final polymer properties were evaluated by dynamic mechanical analysis in shear mode in the temperature range from ?145°C to 200°C. The mechanical properties of the hypoallergenic denture base polymers were validated regarding stiffness (flexural modulus E') and fracture toughness (maximum factor of loading intensity , total work of fracture ) and the effects of monomer composition, kind of resin powder, impact modification by the liquid component, and water immersion on these properties were investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41378. 相似文献
76.
Peter T. Witte Peter H. Berben Susan Boland Evert H. Boymans Dieter Vogt John W. Geus Johannes G. Donkervoort 《Topics in Catalysis》2012,55(7-10):505-511
An innovative BASF catalyst manufacturing technology (NanoSelect?) is introduced which allows production of heterogeneous catalysts with excellent control over metal crystallite sizes. NanoSelect? technology enabled the development of Pd catalysts which are lead-free Lindlar catalyst replacements in alkyne-to-cis-alkene hydrogenations. NanoSelect? Pt catalysts showed excellent chemoselectivity in substituted nitro-arene hydrogenation reactions without build-up of hydroxylamine intermediates. All NanoSelect? produced catalysts show markedly higher activity per gram of metal leading to ten-fold less use of precious metal. 相似文献
77.
Per Weslien Tobias Rütting ?sa Kasimir-Klemedtsson Leif Klemedtsson 《Nutrient Cycling in Agroecosystems》2012,94(2-3):249-253
The emissions of the greenhouse gas nitrous oxide (N2O) were measured from a non nitrogen fertilized carrot (Daucus carota ssp. sativa) field on an organic soil in Sweden during one cropping and post-harvest season. The cumulative emission during the measuring period of 149?days was 41 (±2.8) kg N2O ha?1. Dividing the measuring period into a cropping and a post-harvest period revealed that the presence of carrots strongly stimulated N2O emissions, as the emission during the cropping period was one order of magnitude higher compared to the post-harvest period. The N2O emission from the carrot field were higher than fluxes reported from cereal crop and grass production, but in the same order as reported fluxes from vegetable cropping on organic soils. In conclusion, our results indicate that the cultivation of root vegetable, such as carrots, on organic soil can be a high point source for N2O emissions. 相似文献
78.
Tobias Hausmann Jrg Pietruszka Sebastian Schumacher 《Advanced Synthesis \u0026amp; Catalysis》2012,354(10):1847-1860
An exhaustive overview of the field of cyclohexa‐3,5‐diene‐1,2‐trans‐diols is given. Early and recent methods for the formation of the compounds are reviewed and the various syntheses in which the title compounds have been applied are presented. Special emphasis is given to naturally occurring epoxides, which have been the dominant target molecules since the 1970s. Finally, recent advances in biotechnology are highlighted; with the increased availability of the enantiomerically pure cyclohexa‐3,5‐diene‐1,2‐trans‐diols, new synthetic endeavours were initiated. 相似文献
79.
Annika Linke Tobias Linke Reinhard Kohlus 《European Journal of Lipid Science and Technology》2020,122(8)
Microencapsulation aims to protect polyunsaturated fatty acids against oxidation by embedding oil droplets in a solid matrix. In such a system the internal (dissolved and entrapped) and external (in the environment) oxygen can be differentiated. The study aims to quantify the impact of both oxygen sources on the oxidation of microencapsulated fish oil. The impact of the solubilized oxygen in bulk fish oil is investigated by saturating the oil with nitrogen, synthetic air, and pure oxygen. Even though more dissolved oxygen results in more oxidation products, the difference between the oxidation of the nitrogen and air saturated oil is significant but low. For encapsulated fish oil powders, the internal oxygen is modified by preparing oil‐in‐water emulsions under atmospheric and inert conditions. The feed is atomized and spray dried with either nitrogen or air. Powders are stored under vacuum and in vials and the hydroperoxides and anisidine value are determined in the total‐ and encapsulated oil. The internal oxygen has a minor impact, whereas the external oxygen is the main determinant for autoxidation. Apart from oxidizing the non‐encapsulated oil, the external O2 penetrates into the particle and reacts with the encapsulated oil. Practical Applications: Comparing the contribution of the internal and external oxygen to the oxidative stability shows that the internal O2 plays a minor role and can be neglected. This means that the emulsion preparation as well as the spray drying process can be conducted under ambient conditions. An inert production is not extending the shelf life significantly as long as the external O2 determines oxidation. The focus should be on optimizing the diffusion barrier properties of the wall matrix to reduce the penetration of the external oxygen into the particle system. Alternatively, packaging solution reducing the external O2 will extend the shelf life of the microencapsulated oil. 相似文献
80.
Anja S. GoldmannLeonie Barner Michael KauppAndrew P. Vogt Christopher Barner-Kowollik 《Progress in Polymer Science》2012,37(7):975-984
Modular ligation strategies for the functionalization of polymeric microspheres provide new perspectives for their applications in material science. In the current trend article we highlight variable synthetic procedures for generating functional microspheres via orthogonal modular conjugation chemistries. An overview of the different surface chemistries available is provided, followed by surface-sensitive characterization techniques relevant for the microparticles. Finally, we explore future trends in modular orthogonal modification approaches on microparticles and provide an outlook on the perspectives that the field of surface-modification of polymeric microparticles holds. 相似文献