972 resultados para cyclopropane 1,2,3-substitué


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This article gives details of our proposal to replace ordinary chiral SU(3)L×SU(3)R perturbation theory χPT3 by three-flavor chiral-scale perturbation theory χPTσ. In χPTσ, amplitudes are expanded at low energies and small u,d,s quark masses about an infrared fixed point αIR of three-flavor QCD. At αIR, the quark condensate ⟨q¯q⟩vac≠0 induces nine Nambu-Goldstone bosons: π,K,η, and a 0++ QCD dilaton σ. Physically, σ appears as the f0(500) resonance, a pole at a complex mass with real part ≲ mK. The ΔI=1/2 rule for nonleptonic K decays is then a consequence of χPTσ, with a KSσ coupling fixed by data for γγ→ππ and KS→γγ. We estimate RIR≈5 for the nonperturbative Drell-Yan ratio R=σ(e+e−→hadrons)/σ(e+e−→μ+μ−) at αIR and show that, in the many-color limit, σ/f0 becomes a narrow qq¯ state with planar-gluon corrections. Rules for the order of terms in χPTσ loop expansions are derived in Appendix A and extended in Appendix B to include inverse-power Li-Pagels singularities due to external operators. This relates to an observation that, for γγ channels, partial conservation of the dilatation current is not equivalent to σ-pole dominance.

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We present the crystal structures of the SEC14-like domain of supernatant protein factor (SPF) in complex with squalene and 2,3-oxidosqualene. The structures were resolved at 1.75 Å (complex with squalene) and 1.6 Å resolution (complex with 2,3-oxidosqualene), leading in both cases to clear images of the protein/ substrate interactions. Ligand binding is facilitated by removal of the Golgi-dynamics (GOLD) C-terminal domain of SPF, which, as shown in previous structures of the apo-protein, blocked the opening of the binding pocket to the exterior. Both substrates bind into a large hydrophobic cavity, typical of such lipid-transporter family. Our structures report no specific recognition mode for the epoxide group. In fact, for both molecules, ligand affinity is dominated by hydrophobic interactions, and independent investigations by computational models or differential scanning micro-calorimetry reveal similar binding affinities for both ligands. Our findings elucidate the molecular bases of the role of SPF in sterol endo-synthesis, supporting the original hypothesis that SPF is a facilitator of substrate flow within the sterol synthetic pathway. Moreover, our results suggest that the GOLD domain acts as a regulator, as its conformational displacement must occur to favor ligand binding and release during the different synthetic steps.

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HIV-infected women are at increased risk of cervical intra-epithelial neoplasia (CIN) and invasive cervical cancer (ICC), but it has been difficult to disentangle the influences of heavy exposure to HPV infection, inadequate screening, and immunodeficiency. A case-control study including 364 CIN2/3 and 20 ICC cases matched to 1,147 controls was nested in the Swiss HIV Cohort Study (1985-2013). CIN2/3 risk was significantly associated with low CD4+ cell counts, whether measured as nadir (odds ratio (OR) per 100-cell/μL decrease=1.15, 95% CI: 1.08, 1.22), or at CIN2/3 diagnosis (1.10, 95% CI: 1.04, 1.16). An association was evident even for nadir CD4+ 200-349 versus ≥350 cells/μL (OR=1.57, 95% CI: 1.09, 2.25). After adjustment for nadir CD4+, a protective effect of >2-year cART use was seen against CIN2/3 (OR versus never cART use=0.64, 95% CI: 0.42, 0.98). Despite low study power, similar associations were seen for ICC, notably with nadir CD4+ (OR for 50 versus >350 cells/μL= 11.10, 95% CI: 1.24, 100). HPV16-L1 antibodies were significantly associated with CIN2/3, but HPV16-E6 antibodies were nearly exclusively detected in ICC. In conclusion, worsening immunodeficiency, even at only moderately decreased CD4+ cell counts (200-349 CD4+ cells/μL), is a significant risk factor for CIN2/3 and cervical cancer. This article is protected by copyright. All rights reserved.

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A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II)–molybdate solids under hydrothermal conditions. In the multicomponent CuII/Hpz-tr/MoVI system, a diverse set of coordination hybrids, [Cu(Hpz-tr)2SO4]·3H2O (2), [Cu(Hpz-tr)Mo3O10] (3), [Cu4(OH)4(Hpz-tr)4Mo8O26]·6H2O (4), [Cu(Hpz-tr)2Mo4O13] (5), and [Mo2O6(Hpz-tr)]·H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (CuII and MoVI) sources, the temperature, etc., on the reaction products outcome. Complexes 2–4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2–6, the organic ligand behaves as a short [N–N]-triazole linker between metal centers Cu···Cu in 2–4, Cu···Mo in 5, and Mo···Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for π–π stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250–300 °C. The magnetic measurements were performed for 2–4, revealing in all three cases antiferromagnetic exchange interactions between neighboring CuII centers and long-range order with a net moment below Tc of 13 K for compound 4.

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The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

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Welsch (Projektbearbeiter): Rechenschaftslegung über die Spendeneinnahmen des Vereins sowie deren Verwendung (Auszahlung von Löhnen für öffentliche Erdarbeiten)

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Vorbesitzer: Abraham Berliner

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"Problem der neueren Philosophie", Vorlesung Wintersemester 1950/51 und Sommersemester 1951, 1) Heft, 78 Blatt und 20 zusätzliche Blätter, eigenhändige Notizen (GS 14, S. 145, 151-152), 2) Friedrich Pollock: Notizen zur Volesung Max Horkheimers, Wintersemester 1950/51), eigenhändige Notizen, 9 Blatt; "Philosophie im 17. Jahrhundert (insbes. Spinoza)", Vorlesung Winteremester 1951/52, 1) Heft 1, 17 Blatt und 2 zusätzliche Blätter, eigenhändige Notizen, 2) Heft 2, 46 Blatt, davon 3 leer, und 15 zusätzliche Blätter, eigenhändige Notizen; "Philosophie im 18. Jahrhundert", Vorlesung Sommersemester 1952, 1 Heft mit eigenhändigen Notizen, 64 Blatt, davon 30 leer, und 44 zusätzliche Blätter;

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"Einführung in die Philosophie", Vorlesung, Wintersemester 1956/57, 1 Heft mit eigenhändigen Notizen, 16 Blatt, davon 4 leer, mit 1 zusätzlichem Blatt; "Geschichte des Materialismus (ausgewählte Kapitel)" (GS 13, S. 397-451), Vorlesung, Sommersemester 1957, 1. Max Horkheimer, eigene Notizen, 1 Heft ohne Einband, 16 Blatt und 3 zusätzliche Blätter, 2. Hilmar Tillack: Ausgearbeitete Nachschrift der Vorlesung Max Horkheimers, Typoskript, 46 Blatt; "Society and Value", Vorlesung Chicago 1957, Heft 1: eigene Notizen, 60 Blatt, davon 13 leer, und zusätzliche 6 Blätter; Heft 2: eigene Notizen, 45 Blatt, davon 30 leer, und zusätzlich 8 Blatt; darin auch enthält: Begriff der Seele seit Leibniz", Vorlesung, Sommersemester 1958;

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"Über den Begriff der Seele seit Leibniz" (GS 13, S. 515-569), Vorlesung Sommersemester 1958, Hilmar Tillack: Ausgearbeitete Nachschrift der Vorlesung von Max Horkheimer, Typoskript, 49 Blatt; "Einleitung in die Philosophie", Vorlesung Sommersemester 1959, Max Horkheimer: 1 Heft, eigene Notizen, 8 Blatt, davon 4 leer und 3 zusätzliche Blätter; Hilmar Tillack: Ausgearbeitete Nachschrift der Vorlesung Max Horkheimers, Typoskript 107 Blatt; "Die Aufklärung" (GS 13, S. 570-645), Vorlesung und Proseminar Wintersemester 1959/60, Max Horkheimer: eigenhändige Notizen, 1 Heft, 40 Blatt, davon 23 leer und 21 zusätzliche Blätter (GS 14, S. 146, 145-155); Hilmar Tillack: Ausgearbeitete Nachschrift der Vorlesung Max Horkheimers, Typoskript 70 Blatt;

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"On the Sociology of Class Relations" (GS 12, S.75-104); 1. 1943 Aufsatz. a) Typoskript mit handschriftlichen Korrekturen, 34 Blatt b) Typoskript mit eigenhändigen Korrekturen, 31 Blatt c) Typoskript, 31 Blatt und eigenhändigen Ergänzungen, 1 Blatt d) Typoskript mit eigenhändigen Korrekturen, 26 Blatt; 2. Franz Neumann: 1 eigenhändiger Brief mit Unterschrift an Max Horkheimer mit Anmerkungen zum Aufsatz, ohne Ort, 30.09.1943, 11 Blatt; "The Psychology of Nazidom" (GS 5, S. 354-359); 1. Buchbesprechung von "Is Germany Inucable?" von Richard M. Brickner; veröffentlicht in: "The New Leader", 14.08.1943. a)Typoskript, 7 Blatt b) Typoskript mit eigenhändigen und handschriftlichen Korrekturen, 7 Blatt c) Zeitungsdruck, 3 Exemplare; 2. "What Shall We Do With Germany? A Panel Discussion of 'Is Germany Incurable?'". Zeitungsausschnitte aus : "The Saturday Review of Literature", 29.05.1343, 6 Blatt;