Neocarzinostatin chromophore: structural, mechanistic, and synthetic studies

Neocarzinostatin chromophore 1 is the active component of the antitumor antibiotic neocarzinostatin (NCS). The chromophore reacts with thiols to form a highly strained cumulene-enyne species which rapidly rearranges to a biradical intermediate which can abstract hydrogen atoms from DNA, leading to strand cleavage. DNA damage is the proposed source of biological activity for NCS. The structure of the methyl thioglycolate monoadduct 2 of NCS chromophore, including the absolute stereochemistry, was determined by NMR studies. The presence of the cumulene-enyne intermediate and the rearrangement to a biradical were supported by data from low temperature NMR investigations. Also included are synthetic approaches to NCS chromophore model compounds based on intramolecular addition of an acetylide to an aldehyde.

Water chemistry and osmoregulation in some arthropods, especially Malacostraca

This article briefly summarises some chief characteristics of osmoregulatory systems in malacostracan crustaceans, evolved to combat hydration, and the limitations thereby imposed on the salinity tolerance and distribution of these animals.

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

Structural, optical and electrical properties of ZnO films grown on c-plane sapphire and (100)gamma-LiAlO2 by pulse laser deposition

ZnO thin films were grown on single-crystal gamma-LiAlO2 (LAO) and sapphire (0001) substrate by pulsed laser deposition (PLD). The structural, optical and electrical properties of ZnO films were investigated. The results show that LAO is more suitable for fabricating ZnO films than sapphire substrate and the highest-quality ZnO film was attained on LAO at the substrate temperature of 550 degrees C. However, when the substrate temperature rises to 700 degrees C, lithium would diffuse from the substrate (LAO) into ZnO film which makes ZnO film on LAO becomes polycrystalline without preferred orientation, the stress in ZnO film increases dominantly and the resistivity of the film decreases exponentially. (c) 2005 Elsevier B.V. All rights reserved.

Structural, morphological and optical properties of ZnO thin films grown on gamma-LiAlO2 substrate by pulsed laser deposition

ZnO thin films were deposited on the substrates of (100) gamma-LiAlO2 at 400, 550 and 700 degrees C using pulsed laser deposition (PLD) with the fixed oxygen pressure of 20 Pa, respectively. When the substrate temperature is 400 degrees C, the grain size of the film is less than 1 mu m observed by Leitz microscope and measured by X-ray diffraction (XRD). As the substrate temperature increases to 550 degrees C, highly-preferred c-orientation and high-quality ZnO film can be attained. While the substrate temperature rises to 700 degrees C, more defects appears on the surface of film and the ZnO films become polycrystalline again possibly because more Li of the substrate diffused into the ZnO film at high substrate temperature. The photoluminescence (PL) spectra of ZnO films at room temperature show the blue emission peaks centered at 430 nm. We suggest that the blue emission corresponds to the electron transition from the level of interstitial Zn to the valence band. Meanwhile, the films grown on gamma-LiAlO2 (LAO) exhibit green emission centered at 540 nm, which seemed to be ascribed to excess zinc and/or oxygen vacancy in the ZnO films caused by diffusion of Li. from the substrates into the films during the deposition.

Influences of Al doping concentration on structural, electrical and optical properties of Zn0.95Ni0.05O powders

Nanocrystalline Zn0.95 - xNi0.05AlxO (x = 0.01, 0.02, 0.05 and 0.10) diluted magnetic semiconductors have been synthesized by an auto-combustion method. X-ray diffraction measurements indicate that all Al-doped Zn0.95Ni0.05O samples have the pure wurtzite structure. Transmission electron microscope analyses show that the as-synthesized powders are of the size 40 - 45 nm. High-resolution transmission electron microscope, energy dispersive spectrometer and X-ray photoemission spectroscope analyses indicate that Ni2+ and Al3+ uniformly substitute Zn2+ in the wurtzite structure without forming any secondary phases. The Al doping concentration dependences of cell parameters (a and c), resistance and the ratio of green emission to UV emission have the similar trends. (c) 2007 Elsevier B.V. All rights reserved.

Degeneration of postovulatory follicles in the Iberian sardine Sardina pilchardus: structural changes and factors affecting resorption

Inaccuracy in the aging of postovulatory follicles (POFs) and in estimating the effect of temperature on the resorption rate of POFs may introduce bias in the determination of the daily spawning age classes with the daily egg production method (DEPM). To explore the above two bias problems with f ield-collected European pilchard (Sardina pilchardus, known regionally as the Iberian sardine), a method was developed in which the time elapsed from spawning (POF age) was estimated from the size of POFs (i.e., from the cross-sectional area in histological sections). The potential effect of the preservative type and embedding material on POF size and the effect of ambient water temperature on POF resorption rate are taken into account with this method. A highly significant loglinear relationship was found between POF area and age; POF area shrank by approximately 50% per day. POFs were also shown to shrink faster at higher temperatures (approximately 3% per degree), but this temperature effect is unlikely to be an important source of bias in the assignment of females to daily spawning classes. The embedding material was also shown to influence the size of POFs, the latter being significantly larger in resin than in paraffin sections. In conclusion, the size of POFs provides an indirect, reliable estimation of the time elapsed from spawning and may thus be used to test both the validity of POF staging criteria for identifying daily classes of spawners and the effect of other factors (such as temperature and laboratory processing) in applications of the DEPM to S. pilchardus and other fish species.