Imido-osmium(VIII) compounds in organic synthesis: aminohydroxylation and diamination reactions

Imido complexes of osmium tetroxide are versatile compounds for olefin functionalisation. This tutorial review offers a brief historical overview on these compounds and discusses the electronic properties and reactivities of isolated imido osmium compounds in what had been the original stoichiometric aminohydroxylation reaction. The recently emerging catalytic Sharpless aminohydroxylation is discussed with special emphasis on mechanistic details. The final section deals with diamination of olefins, which relies on the chemistry of bisimido and trisimido osmium complexes.     

Direct Addition of Grignard Reagents to Aliphatic Carboxylic Acids Enabled by Bulky turbo-Organomagnesium Anilides

The synthesis of ketones through addition of organometallic reagents to aliphatic carboxylic acids is a straightforward strategy that is limited to organolithium reagents. More desirable Grignard reagents can be activated and controlled with a bulky aniline-derived turbo-Hauser base. This operationally simple procedure allows the straightforward preparation of a variety of aliphatic and perfluoroalkyl ketones alike from functionalized alkyl, aryl and heteroaryl Grignard reagents.     

Nutritional Value and Preventive Role of Nigella sativa L. and Its Main Component Thymoquinone in Cancer: An Evidenced-Based Review of Preclinical and Clinical Studies

In recent times, scientific attention has been paid to different foods and their bioactive components for the ability to inhibit the onset and progress of different types of cancer. Nigella sativa extract, powder and seed oil and its main components, thymoquinone and α-hederin, have showed potent anticancer and chemosensitizing effects against various types of cancer, such as liver, colon, breast, renal, cervical, lung, ovarian, pancreatic, prostate and skin tumors, through the modulation of various molecular signaling pathways. Herein, the purpose of this review was to highlight the anticancer activity of Nigella sativa and it constitutes, focusing on different in vitro, in vivo and clinical studies and projects, in order to underline their antiproliferative, proapoptotic, cytotoxic and antimetastatic effects. Particular attention has been also given to the synergistic effect of Nigella sativa and it constitutes with chemotherapeutic drugs, and to the synthesized analogs of thymoquinone that seem to enhance the chemo-sensitizing potential. This review could be a useful step towards new research on N. sativa and cancer, to include this plant in the dietary treatments in support to conventional therapies, for the best achievement of therapeutic goals.     

Polymer Lamellae as Reaction Intermediates in the Formation of Copper Nanospheres as Evidenced by In Situ X‐ray Studies

The classical nucleation theory (CNT) is the most common theoretical framework used to explain particle formation. However, nucleation is a complex process with reaction pathways which are often not covered by the CNT. Herein, we study the formation mechanism of copper nanospheres using in situ X‐ray absorption and scattering measurements. We reveal that their nucleation involves coordination polymer lamellae as pre‐nucleation structures occupying a local minimum in the reaction energy landscape. Having learned this, we achieved a superior monodispersity for Cu nanospheres of different sizes. This report exemplifies the importance of developing a more realistic picture of the mechanism involved in the formation of inorganic nanoparticles to develop a rational approach to their synthesis.     

Exclusive measurement of the pp --> pppi(+)pi(-) reaction near threshold

The pp-->pp pi(+) pi(-) reaction has been measured exclusively near threshold at CELSIUS. The total cross sections are nearly an order of magnitude lower than expected from previous inclusive measurements. The differential cross sections reveal pp-->pp(*)(1440)-->pp sigma = pp(pi(+)pi(-))(I = l = 0) as the dominant process as well as significant contributions from p(*)-->Delta(++)pi(-)-->psigma. The observed anisotropy in the proton angular dependence is consistent with heavy-meson exchange. In the invariant mass spectra, no narrow structures of statistical relevance (3sigma) are found.     

New aspects of yielding in semicrystalline polymers related to microstructure: Branched polyethylene

The application of thermodynamics of eutectoid copolymers and a generalized Tabor-relation to relationships between mechanical properties (microhardness, yield stress) and microstructure in semicrystalline polymers is considered. The approach is illustrated by results on melt-crystallized low density polyethylene, investigated near the yield point at different temperatures. The success of the approach emphasizes that semicrystalline polymers, despite being viscoelastic hetereogeneous systems, give rise to a yielding process entailing the irreversible deformation of a larger number of crystals within cooperative super-structure units. Microhardness provides, within this context, a unique measure of the crystal size average. Comparison of calculated and experimental data favors the view of deformed crystals containing basal defective surface boundaries (meso-crystals) which yield cooperatively.Dedicated to Professor Dr. Dr. h. c. Armin Weiss on the occasion of his 60th birthday.     

Investigation of the superstructure of native collagen by a combination of small angle X-ray scattering,electron microscopy and light diffraction

Summary It is shown that there exists a direct correlation between the light diffraction pattern of an electron-microscopical picture and the X-ray small angle scattering. By this means it can be proved for native collagen prepared by a special method that the density pattern of stained samples imaged in the electron microscopy is identical with the density pattern available from moist fibres. The reflex intensities of the small angle X-ray scattering are taken for calculating the density structure whereby the necessary phases are delivered by the electron microscopic examination combined with light diffraction.

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Zusammenfassung Zwischen der Lichtbeugung an elektronenmikroskopischen Bildern und der Röntgenkleinwinkelstreuung wird die direkte Korrespondenz aufgezeigt. Hierbei kann erwiesen werden, daß das elektronenmikroskopische Bild von speziell präpariertem, nativem Kollagen jene Dichtestruktur widerspiegelt, welche auch im feuchten Zustand vorliegt.Aus den Intensitäten der Röntgenbeugung wird die Elektronendichteverteilung errechnet. Die hierzu erforderlichen Phasen können über die Lichtbeugung aus dem elektronenmikroskopischen Bild entnommen werden.

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With 17 figures