Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

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.

Rede des Studenten Edmund Monecke bei seiner Verurtheilung in zweiter Instanz zu 2 1/2 Jahren Festungsstrafe und Verlust der National-Kokarde (im Juli 1848): Wenn man heute dem preußischen Volke das ruhige klare Auge eines Geschichtsforschers leihen könnte ...

Welsch (Projektbearbeiter): Rechtfertigung des Angeklagten gegen den Vorwurf der Majestätsbeleidigung

Transfer and effects of 1,2,3,5,7-pentachloronaphthalene in an experimental food chain.

Polychlorinated naphthalenes are environmentally relevant compounds that are measured in biota at concentrations in the μg/kg lipid range. Despite their widespread occurrence, literature data on the accumulation and effects of these compounds in aquatic ecosystems are sparsely available. The goal of this study was to gain insights into the biomagnification and effects of 1,2,3,5,7-pentachloronaphthalene (PeCN52) in an experimental food chain consisting of benthic worms and juvenile rainbow trout. Worms were contaminated with PeCN52 by passive dosing from polydimethylsiloxane silicone. The contaminated worms were then used to feed the juvenile rainbow trout at 0.12, 0.25 or 0.50 μg/g fish wet weight/day, and the resulting internal whole-body concentrations of the individual fish were linked to biological responses. A possible involvement of the cellular detoxification system was explored by measuring PeCN52-induced expression of the phase I biotransformation enzyme gene cyp1a1 and the ABC transporter gene abcb1a. At the end of the 28-day study, biomagnification factors were similar for all dietary intake levels with values between 0.5 and 0.7 kg lipid(fish)/kg lipid(worm). The average uptake efficiency of 60% indicated that a high amount of PeCN52 was transferred from the worms to the fish. Internal concentrations of up to 175 mg/kg fish lipid in the highest treatment level did not result in effects on survival, behavior, or growth of the juvenile trout, but were associated with the induction of phase I metabolism which was evident from the significant up-regulation of cyp1a1 expression in the liver. In contrast, no changes were seen in abcb1a transcript levels.

Role of cytochrome P450 in DNA damage produced by treatment of colon cells with 1,2-dimethylhydrazine

The study of colon cancer has taken advantage of the development of a model in animals in which tumors in the colon are easily induced by chemical treatment. When 1,2-dimethylhydrazine (DMH) is injected into rats tumor growth is observed in colon in preference to other tissues. This observation led us to investigate the Cytochrome P450 system in colon and its participation in the particular “colon sensitivity” to DMH. It has been established that the Cytochrome P450 system participates in the metabolism of DMH and the methyl carbonium product of Cytochrome P450 activation of DMH is responsible for DNA damage which is considered an initial step to carcinogenesis. The Cytochrome P450 system is a reasonable place to search for an explanation of this organotropic effect of DMH and we feel that the knowledge obtained from this study can take us closer to understanding the development of colonic malignancy. In our study we used a human colon cell line (LS174T) treated with DMH. The Cytochrome P450 system in the cells was manipulated with inducers of different isoforms of Cytochrome P450. The effect of DMH on colon cells was measured by determination of O-6-methylguanine which is a DNA adduct derived from the metabolism of this chemical and is associated with development of tumors. Our results support the hypothesis that Cytochrome P450 plays an important role in the damage to cellular DNA by DMH. This damage is increased after induction of Cytochromes P450 1A1 and 2E1. The effect of inhibition of the methyltransferase and glutathione systems on protection against DMH damage in colon demonstrated the importance of the protective role of the former and the lack of effective protection of the latter system. ^

Sterblichkeit der Juden in Wilna in den letzten 5 1/2 Jahren (1911-1916)

Zemach Schabad

Sterblichkeit der Juden in Wilna in den letzten 5 1/2 Jahren (1911-1916)

Zemach Schabad

[Bd 1/2]

Beide Bände in einem Digitalisat

Officielles un allein ächtes, in der kaiserlichen Hofdruckerei zu Bernem gedrucktes, Fest- & Krönungs-Programm : ... zur ... Krönung Seiner närrischen Majestät Kasier Carneval des Ersten in seiner alten & getreuen Närrischen Freien Reichs-, Krönungs- & Wahlstadt Frankfurt am Main an den Tagen und Nächten des 1., 2. und 3. des Martii, anno 1862

unverantwortlich verfasst von Fr. Stoltze

Inc. hebr. 1 Bd. 1/2 - Canon

Bei der Foliierung wurden Blätter übergangen, jetzt foliiert als Bl. 55a, 121a und 137a.

Inc. fragm. Speyer I Nr. 1 - Lectura super Sexto Decretalium. P.1.2

Rubriziert

Na 1 Nachlass Max Horkheimer, 622 - Unterlagen zu einführenden Vorlesungen (p. VIII 41,1-2-VIII 41b)

"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;

Na 1 Nachlass Max Horkheimer, 625 - Unterlagen zu den Vorlesungen "Einführung der Philosophie", "Geschichte des Materialismus" und "Society and Value" (p. VIII 42a-VIII 43,1-2)

"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;