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61.
Jakob Oren Michaela Vardi Rossana Viskin Sarah Abramson Benzion Fuchs 《Helvetica chimica acta》1993,76(3):1182-1193
The title molecules were shown to photorearrange with remarkable selectivity. Wavelength variation steers the rearrangement modes, of which the [1,2]-acyl shift was found to be largely regioselective, diastereoselective, and enantiospecific. Chemical intercorrelation of products and mechanistic studies were carried out all along. The potential significance of these photochemical processes in selective synthetic schemes is discussed. 相似文献
62.
Organotin–Oxido Cluster‐Based Multiferrocenyl Complexes Obtained by Hydrolysis of Ferrocenyl‐Functionalized Organotin Chlorides
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Zhiliang You Robert Möckel Jakob Bergunde Prof. Dr. Stefanie Dehnen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(42):13491-13496
Three organotin–oxido clusters were formed by hydrolysis of ferrocenyl‐functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [RFcSnCl3?HCl] ( C ; RFc = CMe2CH2C(Me)?N?N?C(Me)Fc) and [SnCl6]2? formed {(RFcSnCl2)3[Sn(OH)6]}[SnCl3] ( 3 a ) and {(RFcSnCl2)3[Sn(OH)6]}[PhSeO3] ( 3 b ), bearing an unprecedented [Sn4O6] unit, in a one‐pot synthesis or stepwise through [(RFcSnCl2)2Se] ( 1 ) plus [(RFcSnCl2)SePh] ( 2 ). A one‐pot reaction starting out from FcSnCl3 gave [(FcSn)9(OH)6O8Cl5] ( 4 ), which represents the largest Fc‐decorated Sn/O cluster reported to date. 相似文献
63.
64.
CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation
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Dr. Yehua Jin Dr. Chien‐Hung Yeh Dr. Christian A. Kuttruff Dr. Lars Jørgensen Dr. Georg Dünstl Dr. Jakob Felding Dr. Swaminathan R. Natarajan Prof. Dr. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2015,54(47):14044-14048
Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained. 相似文献
65.
The first total synthesis of the indole alkaloid mersicarpine is reported. Key steps include a beta-dicarbonyl radical cyclization, as well as an oxidation of the benzopyrrole moiety to establish the masked 1,2-dicarbonyl functionality. An X-ray crystal structure and discussion of the 1H NMR behavior of the natural product are also presented. 相似文献
66.
Andrea Preuß Marcus Korb Tobias Rüffer Jörn Bankwitz Colin Georgi Alexander Jakob Stefan E. Schulz Heinrich Lang 《无机化学与普通化学杂志》2020,646(13):670-680
The template synthesis of ethylenediamine ( 1 ) with 2-acetylcyclopentanone ( 2 ) and [Cu(OAc)2 · H2O] ( 5 ) produced [Cu(1-(2-cC5H6(O))C(Me)NCH2)2)] ( 6 ) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine ( 7 , = L H)[1] gave [Cu(μ-OAc)( L )(H2O)]2 ( 8 ). The solid-state structures of 6 and 8 were determined confirming that 8 possesses intra- and intermolecular hydrogen bonds resulting in a dimer formation. The thermal behavior of 6 – 8 was studied by TG and TG-MS. Under oxygen CuO was formed, whereas under Ar Cu/Cu2O ( 6 ) or Cu ( 8 ) was obtained. Complex 6 was used as CVD precursor for Cu and Cu-oxide deposition (substrate temp., 400–500 °C, N2, 60 mL · min–1; O2, 60 mL · min–1; pressure, 0.87–1.5 mbar). The as-obtained deposits show separated particles of different appearance at the substrate surface as evidenced by SEM. Non-volatile 8 was applied as spin-coating precursor for Cu and CuO formation [conc. 0.25 mol · L–1; volume 0.2 mL; 3000 rpm; depos. time 2 min; heating rate 50 K · min–1; holding time 60 min (Ar), 120 min (air) at 800 °C]. The samples on silicon consist of granulated particles (Ar) or are non-dense with a grainy topography (air). EDX and XPS measurements confirmed the formation of Cu (Ar) or CuO (O2) with up to 13 mol-% C impurity. 相似文献
67.
68.
Emilio Celotti Georgios Lazaridis Jakob Figelj Yuri Scutaru Andrea Natolino 《Molecules (Basel, Switzerland)》2022,27(1)
The oxidation processes of white wines can occur during storage and commercialization due to several factors, and these can negatively affect the color, aroma, and quality of the wine. Wineries should have faster and simpler methods that provide valuable information on oxidation stability of wines and allow fast decision-making procedures, able to trigger suitable technological interventions. Using a portable prototype instrument for light irradiations at different wavelengths and times was considered and evaluated on sensorial, spectrophotometric, and colorimetric parameters of white wines. The sensorial analysis revealed that white and light blue were the most significant, after only 1 h of irradiation. The experimental results showed that hydrogen peroxide could enhance the effect of light treatment, allowing a contemporary evaluation of the oxidation stability of wine against light and chemical stresses. As expected, a good correlation (R2 > 0.89) between optical density at 420 nm and b* parameter was highlighted. The synergic effect of light and H2O2 was also studied on the hydrolyzable and condensed tannins’ additions to white wine. The proposed methodology could be used to evaluate the oxidative stability of white wines, but also to evaluate the effect of some oenological adjuvants on wine stability. 相似文献
69.
Prof. Dr. Tunga Salthammer Friederike Monegel Nicole Schulz Dr. Erik Uhde Prof. Dr. Stefan Grimme Jakob Seibert Prof. Dr. Uwe Hohm Dr. Wolf-Ulrich Palm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):1046-1056
The chemical background of olfactory perception has been subject of intensive research, but no available model can fully explain the sense of smell. There are also inconsistent results on the role of the isotopology of molecules. In experiments with human subjects it was found that the isotope effect is weak with acetone and D6-acetone. In contrast, clear differences were observed in the perception of octanoic acid and D15-octanoic acid. Furthermore, a trained sniffer dog was initially able to distinguish between these isotopologues of octanoic acid. In chromatographic measurements, the respective deuterated molecule showed weaker interaction with a non-polar liquid phase. Quantum chemical calculations give evidence that deuterated octanoic acid binds more strongly to a model receptor than non-deuterated. In contrast, the binding of the non-deuterated molecule is stronger with acetone. The isotope effect is calculated in the framework of statistical mechanics. It results from a complicated interplay between various thermostatistical contributions to the non-covalent free binding energies and it turns out to be very molecule-specific. The vibrational terms including non-classical zero-point energies play about the same role as rotational/translational contributions and are larger than bond length effects for the differential isotope perception of odor for which general rules cannot be derived. 相似文献
70.
Employing a simple hydrophobic-polar heteropolymer model, we compare thermodynamic quantities obtained from Andersen and Nosé-Hoover molecular dynamics as well as replica-exchange Monte Carlo methods. We find qualitative correspondence in the results, but serious quantitative differences using the Nosé-Hoover chain thermostat. For analyzing the deviations, we study different parameterizations of the Nosé-Hoover chain thermostat. Autocorrelations from molecular dynamics and Metropolis Monte Carlo runs are also investigated. 相似文献