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131.
Regio‐ and Enantio‐selective Chemo‐enzymatic C−H‐Lactonization of Decanoic Acid to (S)‐δ‐Decalactone
Jack Manning Michele Tavanti Joanne L. Porter Nico Kress Sam P. DeVisser Nicholas J. Turner Sabine L. Flitsch 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(17):5724-5727
The conversion of saturated fatty acids to high value chiral hydroxy‐acids and lactones poses a number of synthetic challenges: the activation of unreactive C?H bonds and the need for regio‐ and stereoselectivity. Here the first example of a wild‐type cytochrome P450 monooxygenase (CYP116B46 from Tepidiphilus thermophilus) capable of enantio‐ and regioselective C5 hydroxylation of decanoic acid 1 to (S)‐5‐hydroxydecanoic acid 2 is reported. Subsequent lactonization yields (S)‐δ‐decalactone 3 , a high value fragrance compound, with greater than 90 % ee. Docking studies provide a rationale for the high regio‐ and enantioselectivity of the reaction. 相似文献
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Guochao Qi Sam Zhang Khiam Aik Khor Xianting Zeng Chunming Liu Lwin Lwin Ma 《Applied Surface Science》2008,255(2):304-307
Magnesium is one of the most important bivalent ions associated with biological apatite. A series of magnesium-substituted calcium apatite coatings (Ca10−xMgx)(PO4)6(OH)2, where x = 0, 0.50, 1.00, 1.50 and 2.00, are synthesized onto Ti6Al4V substrate by sol-gel dip-coating method to determine how magnesium influences the synthesis and the resulting structural and biological properties. X-ray diffraction (XRD) analysis shows that the incorporation of magnesium helps formation of Mg-containing β-TCP (β-TCMP) phase. X-ray photoelectron spectroscopy (XPS) is used to study the chemical composition and the results show that the apatite structure can only host magnesium less than ∼2.4 wt.% beyond which magnesium aggregates on the surfaces. The incorporation of magnesium slows down the dissolution of Ca2+ from the coating. The in vitro behavior of the coatings is evaluated with human osteosarcoma MG63 cells for cell morphology and proliferation. Similar cell morphologies are observed on all coatings. The cell proliferation results show that the incorporation of magnesium up to x = 2 has no adverse effect on cell growth. 相似文献
134.
Auditory functional magnetic resonance imaging (fMRI) requires quantification of sound stimuli in the magnetic environment and adequate isolation of background noise. We report the development of two novel sound measurement systems that accurately measure the sound intensity inside the ear, which can simultaneously provide the similar or greater amount of scanner- noise protection than ear-muffs. First, we placed a 2.6 x 2.6-mm microphone in an insert phone that was connected to a headphone [microphone-integrated, foam-tipped insert-phone with a headphone (MIHP)]. This attenuated scanner noise by 37.8+/-4.6 dB, a level better than the reference amount obtained using earmuffs. The nonmetallic optical microphone was integrated with a headphone [optical microphone in a headphone (OMHP)] and it effectively detected the change of sound intensity caused by variable compression on the cushions of the headphone. Wearing the OMHP reduced the noise by 28.5+/-5.9 dB and did not affect echoplanar magnetic resonance images. We also performed an auditory fMRI study using the MIHP system and presented increase in the auditory cortical activation following 10-dB increment in the intensity of sound stimulation. These two newly developed sound measurement systems successfully achieved the accurate quantification of sound stimuli with maintaining the similar level of noise protection of wearing earmuffs in the auditory fMRI experiment. 相似文献
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Dr. Cédric Colomban Anthonio H. Tobing Gourab Mukherjee Dr. Chivukula V. Sastri Dr. Alexander B. Sorokin Dr. Sam P. de Visser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(63):14320-14331
The biodegradation of compounds with C−F bonds is challenging due to the fact that these bonds are stronger than the C−H bond in methane. In this work, results on the unprecedented reactivity of a biomimetic model complex that contains an N-bridged diiron-phthalocyanine are presented; this model complex is shown to react with perfluorinated arenes under addition of H2O2 effectively. To get mechanistic insight into this unusual reactivity, detailed density functional theory calculations on the mechanism of C6F6 activation by an iron(IV)-oxo active species of the N-bridged diiron phthalocyanine system were performed. Our studies show that the reaction proceeds through a rate-determining electrophilic C−O addition reaction followed by a 1,2-fluoride shift to give the ketone product, which can further rearrange to the phenol. A thermochemical analysis shows that the weakest C−F bond is the aliphatic C−F bond in the ketone intermediate. The oxidative defluorination of perfluoroaromatics is demonstrated to proceed through a completely different mechanism compared to that of aromatic C−H hydroxylation by iron(IV)-oxo intermediates such as cytochrome P450 Compound I. 相似文献
138.
Dr. Sam P. de Visser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5308-5327
Mononuclear iron-containing enzymes are highly versatile oxidants that often react stereospecifically and/or regioselectively with substrates. Combined experimental and computational studies on heme monooxygenases, nonheme iron dioxygenases and halogenases have revealed the intricate details of the second-coordination sphere, which determine this specificity and selectivity. These second-coordination sphere effects originate from the positioning of the substrate and oxidant, which involve the binding of the co-factors and substrate into the active site of the protein. In addition, some enzymes affect the selectivity and reactivity through charge-stabilization from nearby bound cations/anions, an induced electric field or through the positioning of salt bridges and hydrogen-bonding interactions to first-coordination sphere iron ligands and/or the substrate. Examples of all of these second-coordination sphere effects in iron-containing enzymes and how these influence structure and reactivity are given. 相似文献
139.
Stephanie M. Delgado Sam C. P. Norris Andrea M. Kasko 《Journal of polymer science. Part A, Polymer chemistry》2022,60(5):825-841
Hydrogels are attractive materials for generating 4D shapes due to their ability to undergo pronounced volume changes in response to several stimuli, including light. We previously reported shape-changing hydrogels actuated by long-wave UV and visible light in the presence of live cells using poly(ethylene glycol) macromers incorporating different photodegradable ortho-nitrobenzyl (o-NB) groups. In this comprehensive study, we determine the effect of chemical structure of different o-NB macromers (which influences molar absorptivity and rate constant of degradation), composition (macromer weight percent), fabrication design (initial gel thickness) and environment (ionic strength of solution) on light-induced hydrogel folding. We demonstrate successful photopolymerization and subsequent photodegradation of hydrogels, multistep folding, and live-cell encapsulation. This hydrogel system may be useful as new tool in stem cell differentiation and developmental biology research, facilitating the in vitro investigation of processes that are sensitive to both physical and temporal stimuli. 相似文献
140.
Back Cover: Integrated Transmission Electron and Single‐Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle (Angew. Chem. Int. Ed. 1/2018) 下载免费PDF全文