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71.
72.
Gonzalo Angulo Dr. Jakob Grilj Eric Vauthey Prof. Luis Serrano‐Andrés Prof. Òscar Rubio‐Pons Dr. Patrice Jacques Prof. 《Chemphyschem》2010,11(2):480-488
The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high‐level ab initio CASPT2 calculations of the singlet‐ and triplet‐state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin–orbit coupling terms. The initially populated singlet ππ* state is shown to decay through internal conversion and intersystem crossing processes via intermediate nπ* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversion rates and low fluorescence quantum yields in nonpolar media. The presence of a singlet–triplet crossing near the singlet ππ* minimum and the large spin–orbit coupling terms also rationalize the high intersystem crossing rates. A phenomenological kinetic scheme is proposed that accounts for the decrease in internal conversion and intersystem crossing (i.e. the very large experimental crescendo of the fluorescence quantum yield) with the increase of solvent polarity. 相似文献
73.
A broadly useful acid-labile traceless azido linker for the solid-phase synthesis of NH-1,2,3-triazoles is presented. A variety of alkynes were efficiently immobilized on a range of polymeric supports by Cu(I)-mediated azide-alkyne cycloadditions. Supported triazoles showed excellent compatibility with subsequent peptide chemistry. Release of pure material (typically >95%) from the solid support was readily achieved by treatment with aqueous TFA. 相似文献
74.
We provide two sharp sufficient conditions for immersed Willmore surfaces in $\mathbb{R }^3$ to be already minimal surfaces, i.e. to have vanishing mean curvature on their entire domains. These results turn out to be particularly suitable for applications to Willmore graphs. We can therefore show that Willmore graphs on bounded $C^4$ -domains $\overline{\varOmega }$ with vanishing mean curvature on the boundary $\partial \varOmega $ must already be minimal graphs, which in particular yields some Bernstein-type result for Willmore graphs on $\mathbb{R }^2$ . Our methods also prove the non-existence of Willmore graphs on bounded $C^4$ -domains $\overline{\varOmega }$ with mean curvature $H$ satisfying $H \ge c_0>0 \,{\text{ on }}\, \partial \varOmega $ if $\varOmega $ contains some closed disc of radius $\frac{1}{c_0} \in (0,\infty )$ , and they yield that any closed Willmore surface in $\mathbb{R }^3$ which can be represented as a smooth graph over $\mathbb{S }^2$ has to be a round sphere. Finally, we demonstrate that our results are sharp by means of an examination of some certain part of the Clifford torus in $\mathbb{R }^3$ . 相似文献
75.
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
76.
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
77.
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
78.
CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation 下载免费PDF全文
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
79.
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
80.
Frank Abild-Pedersen Ole Lytken Jakob Engbk Gunver Nielsen Ib Chorkendorff Jens K. Nrskov 《Surface science》2005,590(2-3):127-137
We have, theoretically and experimentally, investigated the dissociation of methane on the terraces and steps of a Ni(1 1 1) surface. Using Density Functional Theory (DFT) total energy calculations combined with Ultra High Vacuum (UHV) experiments, we find that the steps exhibit a higher activity than the terraces. We have, furthermore, investigated how carbon and sulfur present on the surface will deactivate the steps, leaving only the terraces active. We find the intrinsic sticking probabilities of methane on the steps and terraces at 500 K to be 2.8 × 10−7 for the steps and 2.1 × 10−9 for the terraces, in complete agreement with our calculated difference in activation energy of 17 kJ/mol. 相似文献