Synthetic Matching of Complex Monoterpene Indole Alkaloid Chemical Space

Monoterpene indole alkaloids (MIAs) are endowed with high structural and spatial complexity and characterized by diverse biological activities. Given this complexity-activity combination in MIAs, rapid and efficient access to chemical matter related to and with complexity similar to these alkaloids would be highly desirable, since such compound classes might display novel bioactivity. We describe the design and synthesis of a pseudo-natural product (pseudo-NP) collection obtained by the unprecedented combination of MIA fragments through complexity-generating transformations, resulting in arrangements not currently accessible by biosynthetic pathways. Cheminformatic analyses revealed that both the pseudo-NPs and the MIAs reside in a unique and common area of chemical space with high spatial complexity-density that is only sparsely populated by other natural products and drugs. Investigation of bioactivity guided by morphological profiling identified pseudo-NPs that inhibit DNA synthesis and modulate tubulin. These results demonstrate that the pseudo-NP collection occupies similar biologically relevant chemical space that Nature has endowed MIAs with.     

Transient Hg,Ba+, Ca+ and Y+ Optical Emission Lines of a Mercury HID Lamp Exposed to X-Ray: Thermal Analysis of the Tungsten Electrode with Emissive Mixture Based on Barium,Calcium and Yttrium

Plasma Chemistry and Plasma Processing - A study is made on optical emission spectrum modification during X-ray exposure, in the case of a high-pressure mercury discharge lamp operated at several...     

Transamination Studies on N-(1-Alkenylthio)phthalimides and Related Compounds. Synthesis of 1-Alkenesulfenamides and 1-Alkenesulfonamides(1)

In an attempt to develop a method for the general preparation of 1-alkenesulfenamides, some N,N-bis(trimethylsilyl)-1-alkenesulfenamides (4) were converted to a number of nitrogen functionalized analogs through desilylation and acylation procedures. Mono- and dibenzoylated derivatives 5aand 6a did not undergo transamination reactions with simple amines. Transamination reactions could be achieved once compounds 4 were converted to thiophthalimides 7. The transamination products 8 are unstable to chromatography, but could be oxidized to 1-alkenesulfonamides 9 using MCPBA. Some of the sulfenamides 8 may be stable to distillation. 3-(Alkenylthioimino)phthalides 11, isomers of thiophthalimides 7, also react with amines, but the process of ring opening accompanies transamination. It was found that the transamination reactions of 11 probably involve the intermediacy of isomers 7.     

Semicarbazones and thiosemicarbazones,XII: Crystal structure of salicylaldehyde semicarbazone

Summary The crystal and molecular structure of salicylaldehyde semicarbazone was obtained by single crystal X-ray diffraction. The O atom of the semicarbazone fragment isanti to the N atom of the hydrazinic group. The distribution of bond lengths in the semicarbazone fragment indicates delocalization of the -electrons. The crystal structure is stabilized by intra- and intermolecular hydrogen bonds.

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Semicarbazone und Thiosemicarbazone, 12. Mitt.: Die Kristallstruktur des Salicylaldehyd-Semicarbazons

Zusammenfassung Die Kristallstruktur und die molekulare Struktur des Salicylaldehyd-Semicarbazons wurde über Einkristall-Röntgenstreuung ermittelt. Das O-Atom des Semicarbazonteils stehtanti zum N-Atom der Hydrazin-Gruppierung. Die Bindungslängen in der Semicarbazoneinheit zeigen eine Delokalisierung der -Elektronen an. Die Geometrie der Verbindung wird durch stabilisierende intra- und intermolekulare Wasserstoffbrückenbindungen bestimmt.

     

Selective dissolution of TiO2 crystalline phases: Physicochemical characterization and photocatalytic activity

In this study, different commercially available TiO₂ powders (Degussa P25, pure anatase, and rutile) were submitted to selective dissolution treatments, with H₂O₂/NH₄OH and 10% HF, known to remove rutile and anatase from physical mixtures. The aim was to check whether a particular separation method designed to remove a specific crystalline phase influences the properties of the other phase from the mixture or not. More precisely, we have studied how the HF dissolution method designed to selectively remove the anatase affected the physicochemical and photocatalytic properties of rutile. In a similar way, the changes in the anatase properties were studied, after the H₂O₂/NH₄OH treatment, initially used to remove rutile from the mixture. All the samples were characterized by X-ray diffraction, nitrogen adsorption–desorption, transmission electron microscopy, diffuse reflectance (DR) ultraviolet–visible, and Raman spectroscopy. The photocatalytic activity of these powders was tested in the oxidation of p-chlorophenol from water. The selective treatment methods not only dissolved the target phase but also changed some physicochemical and the photocatalytic performances of the other TiO₂ crystalline phase in a considerable manner. These aspects should be taken into account in the studies regarding the synergistic effects of anatase and rutile, especially in reconstructed TiO₂ photocatalysts.     

Cross‐Linked Aptamer–Lipid Micelles for Excellent Stability and Specificity in Target‐Cell Recognition

The specific binding ability of DNA–lipid micelles (DLMs) can be increased by the introduction of an aptamer. However, supramolecular micellar structures based on self‐assemblies of amphiphilic DLMs are expected to demonstrate low stability when interacting with cell membranes under certain conditions, which could lead to a reduction in selectivity for targeting cancer cells. We herein report a straightforward cross‐linking strategy that relies on a methacrylamide branch to link aptamer and lipid segments. By an efficient photoinduced polymerization process, covalently linked aptamer–lipid units help stabilize the micelle structure and enhance aptamer probe stability, further improving the targeting ability of the resulting nanoassembly. Besides the development of a facile cross‐linking method, this study clarifies the relationship between aptamer–lipid concentration and the corresponding binding ability.     

Baer orderings with noninvariant valuation ring

We construct division algebras with involution containing a Baer ordering with noninvariant order ring. This gives a negative answer to a question of Holland, whether the order ring is always invariant under inner automorphisms. Furthermore, we give examples of any index. Previously, the only known examples of division algebras containing Baer orderings were of index 2 ⁿ or of indexp forp a prime of the form 4m + 3. Supported in part by the National Science Foundation.     

Dubrovin valuation rings and Henselization

Supported in part by the National Science Foundation