Synthesis of a model system for the preparation of phloroglucinol containing natural products

A model system for the synthesis of phloroglucinol containing natural products was synthesized. Key steps include a manganic acetate-mediated cyclization and the facile conversion of an alkene into a β-bromoenone.     

Polymer-protected palladium nanoparticles. Morphologies and catalytic selectivities

Colloidal palladium nanocatalysts prepared by in situ reductions of palladium chloride were immobilized and protected by either of two water-soluble polymers. The particle sizes and size distributions of the palladium colloids were determined by transmission electron microscopy. Their selectivities as catalysts were determined by comparing the extents of hydrogenation of carefully chosen pairs of small-molecule olefins. There was found to be high hydrogenation selectivity with regard to cyclic vs. noncyclic olefins. Selectivity was relatively low, however, among olefins that differed only in size (such as hexene vs. octene), or olefins differing only with regard to the positions of the double bonds (such as 1-octene vs. 3-octene). Selectivity could be improved by careful choice of the immobilizing polymer, and by its use at relatively high concentrations.     

Natural anti-HIV agents. Part 3: Litseaverticillols A-H, novel sesquiterpenes from Litsea verticillata

Bioassay directed-fractionation led to the identification of litseaverticillols A-H (1-8) from the leaves and twigs of Litsea verticillata Hance. These new sesquiterpenes possess a unique skeleton that was recently designated as ‘litseane’. The structures of these compounds were determined by spectroscopic means including 1D and 2D NMR data. Structural configurations were determined by ROESY experiments. Mosher ester reactions and optical rotation measurements established the sesquiterpenes 1-8 as racemates. Isolates 1-8 inhibited HIV-1 replication in HOG.R5 cells with IC₅₀ values ranging from 2 to 15 μg/ml (8-58 μM) while affecting the growth of HOG.R5 at concentrations 2-3-fold higher. Based on this data, structure-activity relationships can be discerned, suggesting compounds of this class are good candidates for analog production.     

Möbius aromaticity in [12]annulene: cis-trans isomerization via twist-coupled bond shifting

Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes.     

Hardy Spaces on the Plane and Double Fourier Transforms

We provide a direct computational proof of the known inclusion where is the product Hardy space defined for example by R. Fefferman and is the classical Hardy space used, for example, by E.M. Stein. We introduce a third space of Hardy type and analyze the interrelations among these spaces. We give simple sufficient conditions for a given function of two variables to be the double Fourier transform of a function in and respectively. In particular, we obtain a broad class of multipliers on and respectively. We also present analogous sufficient conditions in the case of double trigonometric series and, as a by-product, obtain new multipliers on and respectively.     

Shelf-life of99mTc(Sn)-pyrophosphate

The effect of the preparation conditions on the in vitro stability of^99mTc (Sn)-pyrophosphate kit solution has been examined. To extend the shelf-life of the preparation, different methods of protection were tested. Nitrogen purging stabilizes the kit for at least 6 h after labeling when the content of^99mTc-pertechnetate raises to about 5%. However, this method is ineffective in the presence of hydrogen peroxide. The protecting ability of two chemicals was also determined. Gentisic acid gave good results. In the presence of 50 g of gentisic acid per ml of the kit the content of pertechnetate was 1–2% throughout the examined time interval. To eliminate the influence of hydrogen peroxide (6 g per ml of the kit) about 100 g of gentisic acid is needed. N, N-diphenyl-p-phenylenediamine (DPPD) performs some protecting effect only when used in the samples protected by nitrogen purging. However its protecting ability is lower that in the case of gentisic acid.     

掺杂镨的纳米二氧化钛光催化降解2,4-二硝基苯酚的研究

以钛酸丁酯为原料,用溶胶-凝胶(sol-gel)法制备了掺杂镨的纳米TiO2粉末.采用X光衍射仪对粉体的物相进行了表征.样品经500 ℃焙烧2 h后,0.5%(摩尔分数)Pr3+-TiO2纳米粉末为单一的锐钛型结构.通过粉体对2,4-二硝基苯酚的降解情况对其光催化活性进行了测试,结果表明与纯TiO2相比,Pr3+-TiO2的光催化活性有较大提高,当Pr3+的掺入量为0.5%(摩尔分数)时催化活性最高.以高压汞灯为光源,2,4-二硝基苯酚的初始浓度为50 mg·L-1,催化剂0.5%(摩尔分数)Pr3+-TiO2投加量为1.0 g·L-1时,2,4-二硝基苯酚的光催化降解效果最好.