Solvation and axial ligation properties of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)

he solvation of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)[Zn(obtpp)], in twelve different solvents results in large red shifts of the B and Q bands of the porphyrin accompanied by enhanced absorbance ratios of the Q bands. These observations are ascribed to the destabilisation of the highest occupied molecular orbital a2u of the porphyrin arising from a flow of charge from the axial ligand to the porphyrin ring through the zinc(II) ion. The binding constants of adducts of [Zn(obtpp)] with neutral bases have been found to be an order of magnitude greater than those observed for the corresponding adducts of (5,10,15,20-tetraphenylporphyrinato)-zinc and vary in the order piperidine > imidazole > pyridine > 3-methylpyridine > pyridine-3-carbaldehyde. The enhanced binding constants and large spectral shifts are interpreted in terms of the electrophilicity of [Zn(obtpp)] induced by the electron-withdrawing bromine substituents in the porphyrin core. The structure of [Zn(obtpp)(PrCN)2] has been determined; it reveals six-co-ordinated zinc(II) with two long Zn–N distance [2.51(4), 2.59(3)Å]. The porphyrin is non-planar and displays a saddle-shaped conformation.

3,12-dinitro-5,10,15,20-tetraphenylporphyrin- an example of a twisted intramolecular charge-transfer system

he porphyrin ring in the title compound, 10,19-dinitro-2,7,12,17-tetraphenyl-21,22,23,24-tetraazapenta-cyclo[16.2.1.1(3,6).1(8,11).1(13,16)]tetracosa-1,3,5,7,9,11(23),-12,14,16,18(21),19-undecaene 0.5-dichloromethane solvate, C44H28N6O4.0.5CH2Cl2, adopts a saddle conformation with neighbouring pyrrole rings tilted with respect to each other. The two nitro groups are situated on alternate pyrrole rings and have their planes angled away from those of the pyrrole rings, thereby indicating that interaction between the porphyrin and nitro groups is slight.

Ligand 5,10,15,20-Tetra(N-methyl-4-pyridyl)porphine (TMPyP4) Prefers the Parallel Propeller-Type Human Telomeric G-Quadruplex DNA over Its Other Polymorphs

The binding of ligand 5,10,15,20-tetra(N-methyl-4-pyridyl)porphine (TMPyP4) with telomeric and genomic G-quadruplex DNA has been extensively studied. However, a comparative study of interactions of TMPyP4 with different conformations of human telomeric G-quadruplex DNA, namely, parallel propeller-type (PP), antiparallel basket-type (AB), and mixed hybrid-type (MH) G-quadruplex DNA, has not been done. We considered all the possible binding sites in each of the G-quadruplex DNA structures and docked TMPyP4 to each one of them. The resultant most potent sites for binding were analyzed from the mean binding free energy of the complexes. Molecular dynamics simulations were then carried out, and analysis of the binding free energy of the TMPyP4-G-quadruplex complex showed that the binding of TMPyP4 with parallel propeller-type G-quadruplex DNA is preferred over the other two G-quadruplex DNA conformations. The results obtained from the change in solvent excluded surface area (SESA) and solvent accessible surface area (SASA) also support the more pronounced binding of the ligand with the parallel propeller-type G-quadruplex DNA.

Cruise Report: Spring 2007 Survey of ecological conditions along the continental shelf off Florida from Anclote Key to West Palm Beach NOAA Ship NANCY FOSTER NF-07-08-NCCOS (May 15 - May 28, 2007)

This cruise report is a summary of a field survey conducted in coastal-ocean waters off Florida from Anclote Key to West Palm Beach and from approximately 1 nautical mile (nm) offshore seaward to the shelf break (100 m). The survey was conducted May 15 - May 28, 2007 on NOAA Ship NANCY FOSTER Cruise NF-07-08-NCCOS. Multiple indicators of ecological condition were sampled synoptically at each of 50 stations throughout the region including 10 stations within the Florida Keys National Marine Sanctuary (FKNMS) using a random probabilistic sampling design. Samples were collected for the analysis of benthic community structure and composition; concentrations of chemical contaminants (metals, pesticides, PAHs, PCBs, PBDEs) in sediments and target demersal biota; nutrient and chlorophyll levels in the water column; and other basic habitat characteristics such as depth, salinity, temperature, dissolved oxygen, pH, sediment grain size, and organic carbon content. The overall purpose of the survey was to collect data to assess the status of ecological condition in coastal-ocean waters of the region, based on these various indicators, and to provide this information as a baseline for determining how environmental conditions may be changing with time. The results will be of value in helping to broaden our understanding of the status of ecological resources and their controlling factors, including impacts of potential ecosystem stressors, in such strategic coastal areas. (PDF contains 34 pages

Synthesis and electrochemical characteristics of lanthanide complexes with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate

Four lanthanide complexes with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate were prepared and characterized by elemental analyses, LR, UV-Visible,H-1 NMR, XPS and molar conductance. The redox properties of the lutetium complex with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate in dichloromethane were studied by cyclic voltammetry.

Investigation of Ground- and Excited-State Photophysical Properties of 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphyrin with Ruthenium Outlying Complexes

The present work employs a set of complementary techniques to investigate the influence of outlying Ru(II) groups on the ground- and excited-state photophysical properties of free-base tetrapyridyl porphyrin (H(2)TPyP). Single pulse and, pulse train Z-scan techniques used M association with laser flash photolysis, absorbance and fluorescence spectroscopy, and fluorescence decay measurements, allowed us to conclude that the presence of outlying Ru(II) groups causes significant changes on both electronic structure and vibrational properties of porphyrin. Such modifications take place mainly due to the activation of. nonradiative decay channels responsible for the emission, quenching, as well as by favoring some vibrational modes in the light absorption process, It is also observed that, differently from what happens when the Ru(II) is placed at the center of the macrocycle, the peripheral groups cause an increase of the intersystem crossing processes, probably due to the structural distortion of the ring that implies a worse spin orbit coupling, responsible for the intersystem crossing mechanism.

Competition between evaporation and fragmentation in nuclear reactions at 15-20 AMeV beam energy

The reactions 32S+58,64Ni are studied at 14.5 AMeV. From this energy on, fragmentation begins to be a dominant process, although evaporation and fission are still present. After a selection of the collision mechanism, we show that important even-odd effects are present in the isotopic fragment distributions when the excitation energy is small. The staggering effect appears to be a universal feature of fragment production, slightly enhanced when the emission source is neutron poor. A closer look at the behavior of isotopic chains reveals that odd-even effects cannot be explained by pairing effects in the nuclear mass alone, but depend in a more complex way on the de-excitation chain.

Na 1 Nachlass Max Horkheimer, 28 - Korrespondenzen mit u.a. Siegfried Kracauer (p. I 14, 115-368)

95 Briefe und Beilagen zwischen Siegfried Kracauer und Max Horkheimer, 1936-1949; 2 Briefe zwischen Else Staudinger vom American Committee for Refugee Scholars, Writers and Artists New York und Max Horkheimer, 10.07.1945, 24.07.1945; 2 Briefe zwischen Meyer Schapiro und Siegfried Kracauer 19.11.1937, 03.12.1937; 2 Briefe von Leo Löwenthal an Schapiro Meyer, 1940, 1941; 1 Brief und 1 Beilage von Max Horkheimer an A. Schütz, 02.08.1940; 1 Brief von Max Horkheimer an Trude Krautheimer, 30.07.1940; 1 Brief von Max Horkheimer an das Hebrew Sheltering and Immigrant Aid New York, 10.06.1940; 2 Briefe ziwschen dem Department of State Washington und Max Horkheimer, 05.04.1939, 1939; 2 Briefe zwischen Betty Drury Max Horkheimer, 05.11.1938, 07.11.1938; 2 Briefe zwischen Margaret Krafft und Max Horkheimer, 1938, 1939; 1 Brief von Gertrud Kurth-Kieslinger an Max Horkheimer, 02.10.1939; 2 Briefe zwischen Werner Kraft und Max Horkheimer, 19.01.1940, 01.03.1940; 1 Brief und 1 Beilage von Friedrich Krause an Max Horkheimer, 05.01.1939; 2 Briefe zwischen Karl Krayl und Max Horkheimer, 201.10.1937, 25.11.1937; 11 Briefe zwischen Ernst Krenek und Max Horkheimer, 1937-1941; 1 Brief von S. Krezel an Max Horkheimer, 12.02.1936; 1 Brief von Charles I. Krieger an Max Horkheimer, 01.08.1940; 1 Brief von H. Kronstein an Max Horkheimer, 20.05.1935; 3 Briefe zwischen Germaine Krull und Max Horkheimer, 1934, 06.09.1937, 1937; 3 Briefe zwischen Lawrence S. Kubie Sekretär der American Psychoanalytic Association, New York und Max Horkheimer, 11.05.1938, 1938; 5 Briefe und Beilagen zwsichen Julius Kühl und Max Horkheimer, 18.10.1939-1940; 1 Brief von Max Horkheimer an Herr Guggenheim, 20.02.1940; 1 Brief von Julius Kühl an die ESKA, 31.03.1945; 4 Briefe zwischen B. Kugelmann und Max Horkheimer, 1934, 1938, 1939; 1 Brief von Georg Kunzel an Max Horkheimer, 01.08.1930;