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121.
Jos I. Urgel Marco Di Giovannantonio Kristjan Eimre Thorsten G. Lohr Junzhi Liu Shantanu Mishra Qiang Sun Amogh Kinikar Roland Widmer Samuel Stolz Max Bommert Reinhard Berger Pascal Ruffieux Carlo A. Pignedoli Klaus Müllen Xinliang Feng Roman Fasel 《Angewandte Chemie (International ed. in English)》2020,59(32):13281-13287
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. Here we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C?C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on‐surface synthesis of cumulene‐containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces. 相似文献
122.
123.
Dominique Fasseur Pascal Cauliez Daniel Couturier Benoît Rigo Sbastien Defretin 《Journal of heterocyclic chemistry》1996,33(6):1951-1957
The 5-methoxycarbonyl group of β-enaminoesters derived from methyl pyroglutamate was transformed into acids, amides and 1,3,4-oxadiazole. 相似文献
124.
Philippe Savarino Emmanuel Colson Guillaume Caulier Igor Eeckhaut Patrick Flammang Pascal Gerbaux 《Molecules (Basel, Switzerland)》2022,27(2)
Saponins are plant and marine animal specific metabolites that are commonly considered as molecular vectors for chemical defenses against unicellular and pluricellular organisms. Their toxicity is attributed to their membranolytic properties. Modifying the molecular structures of saponins by quantitative and selective chemical reactions is increasingly considered to tune the biological properties of these molecules (i) to prepare congeners with specific activities for biomedical applications and (ii) to afford experimental data related to their structure–activity relationship. In the present study, we focused on the sulfated saponins contained in the viscera of Holothuria scabra, a sea cucumber present in the Indian Ocean and abundantly consumed on the Asian food market. Using mass spectrometry, we first qualitatively and quantitatively assessed the saponin content within the viscera of H. scabra. We detected 26 sulfated saponins presenting 5 different elemental compositions. Microwave activation under alkaline conditions in aqueous solutions was developed and optimized to quantitatively and specifically induce the desulfation of the natural saponins, by a specific loss of H2SO4. By comparing the hemolytic activities of the natural and desulfated extracts, we clearly identified the sulfate function as highly responsible for the saponin toxicity. 相似文献
125.
Jérôme Deprince Manuel Bautista Stephan Fritzsche Javier García Timothy Kallman Claudio Mendoza Patrick Palmeri Pascal Quinet 《X射线光谱测定》2020,49(1):29-32
In the present work, we report an investigation of plasma environment effects on the atomic parameters associated with the K-vacancy states in highly charged iron ions within the astrophysical context of accretion disks around black holes. More particularly, the sensitivity of K-line X-ray fluorescence parameters (wavelengths, radiative transition probabilities, and Auger rates) in Fe XVII–Fe XXV ions has been estimated for plasma conditions characterized by an electron temperature ranging from 105 to 107 K and an electron density ranging from 1018 to 1022 cm−3. In order to do this, relativistic multiconfiguration Dirac-Fock atomic structure calculations have been carried out by considering a time averaged Debye-Hückel potential for both the electron–nucleus and electron–electron interactions. 相似文献
126.
Three zinc(II) nitrite coordination polymers, [Zn(4-bpdb)(NO2)2]n (1), {[Zn(3-bpdb)(NO2)]·0.5H2O}n (2) and [Zn(3-bpdh)(NO2)2]n (3), 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, 3-bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene and 3-bpdh = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene} were prepared and characterized by elemental analyses and IR spectroscopy. Compound 3 was structurally characterized by single-crystal X-ray diffraction and is one-dimensional polymer with coordination environments of distorted octahedral, ZnN2O4. The thermal stabilities of compounds 1–3 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Direct calcination of the compounds 1–3 at 600 °C under air atmospheres yields different morphologies of nano-sized ZnO. 相似文献
127.
Depending on the solvothermal reaction conditions, we obtained three different metal-organic frameworks with yttrium(III) as metal component and 2,5-dihdyroxyterepthalic acid (H4dhtp) as bifunctional organic linker: Y2(H2dhtp)3(dmf)4 · (dmf)2 (CPO-29) contains dinuclear, paddle-wheel like inorganic secondary building units (SBUs) connected by the organic linker to a network with α-Po topology, while Y2(H2dhtp)(dhtp)(dmf)2 (CPO-30) and Y2(H2dhtp)(dhtp)(dmf)2(H2O)2 · (H2O)4 (CPO-31) contain one-dimensional inorganic SBUs that differ in how the half- and fully deprotonated ligands are connected to and arranged around them. Only the carboxylic acid groups of the organic linker are deprotonated in CPO-29, while CPO-30 and CPO-31 contain both 2,5-dihydroxyterephthalate (H2dhtp2–) linkers and fully deprotonated 2,5-dioxidoterephthalate (dhtp4–) linkers. All three compounds contain large volumes filled with solvent, but we were able to demonstrate permanence of porosity only for CPO-30. Variable temperature powder X-ray diffraction reveals that CPO-29 and CPO-31 undergo discontinuous phase transitions upon heating, and the flexibility of the framework structure indicated by these might be the reason for the inability to access the pore volume. Desolvated CPO-30 and CPO-31 are polymorphs, whose network structures differ in whether the H2dhtp2– and dhtp4– linkers are located in cis or trans arrangement around the inorganic SBU. 相似文献
128.
Pascal Tixador 《Physica C: Superconductivity and its Applications》2010,470(20):971-979
Europe celebrated last year (2008) the 100-year anniversary of the first liquefaction of helium by H. Kammerling Onnes in Leiden. It led to the discovery of superconductivity in 1911. Europe is still active in the development of superconducting (SC) devices. The discovery of high critical temperature materials in 1986, again in Europe, has opened a lot of opportunities for SC devices by broking the 4 K cryogenic bottleneck. 相似文献
129.