Synthesis of 4-acetylisocoumarin: first total syntheses of AGI-7 and sescandelin

A practical synthetic route to 4-acetylisocoumarins and the first total synthesis of AGI-7 (5) and sescandelin (4) are described. The readily available homophthalate 8 was transformed to the vinylogous amide ester 13 in high overall yield. Upon treatment of 13 with refluxing aqueous formic acid, the desired 4-acetylisocoumarin (5) and its regioisomer 3-methyl-4-formylisocoumarin (17) were produced in a 3:1 ratio. After separation of the desired product (5) from the unwanted minor isomer, the enantioselective reduction of AGI-7 by borane in the presence of Corey's (S)-oxazaborolidine reagent afforded (+)-sescandelin (4) with a 93% ee.     

Isolation of essential oils from tobacco by gas co-distillation/solvent extraction

Summary The essential oils have been isolated from tobacco leaves using a simple gas co-distillation apparatus. The method involves co-distillation with water under the continuous stream of an inert gas with subsequent single solvent extraction of the distillate. The extract is analysed on GC and GC/MS in splitless injection mode without further concentration. The method was evaluated for reproducibility using n-octadecane as an internal standard. The distillation-extraction procedure was reporducible with an average deviation of ±3% for the major constituents. The present method was applied to the analyses of the essential oils of other agricultural products.Dedicated to Dr. L. S. Ettre on the occasion of his 60th birthday.     

A Ca2+-phospholipid-dependent protein kinase from cottonplant shoots

The Ca²⁺-phospholipid-dependent protein kinase from cottonplant shoots was purified by chromatography on DEAE-Sepharose CL-6B, and then on phenyl-Sepharose CL-4B. According to electrophoresis in PAAG, the enzyme was practically homogeneous and had a molecular mass of 57 kDa. In the presence of Ca²⁺ alone, the enzyme was activated to only a slight degree. Under the combined action of Ca²⁺ and a phospholipid the action of the enzyme rose severalfold. A determination of amino acid specificity showed that the protein kinase isolated was a serine- and threonine-specific protein kinase.A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax 627071. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 100–105, January–February, 1994.     

Site-directed exchange studies with combinatorial libraries of nanostructures

We describe a new combinatorial method for studying the exchange between solution adsorbates and nanoscale features within libraries generated via dip-pen nanolithography. Four different compounds, 1-octadecanethiol, 16-mercaptohexadecanoic acid, ferrocene (11-mercaptoundecyl), and ferrocene (11-mercapto-1-oxoundecyl), are studied on amorphous and single-crystal gold substrates. This series of adsorbates allows us to compare the exchange properties of patterns of nanoscale features as a function of composition, feature size, and type of underlying substrate. Moreover, these properties can be compared and contrasted with bulk SAM properties. The novel strategy provides not only a method for initiating site-specific exchange processes but also a way of extracting kinetic information about the rate of such processes in situ.     

Phytochemicals from Echinacea and Hypericum: A Direct Synthesis of Isoligularone

Reaction of trienes with α,β-unsaturated aldehydes produces bicyclic products via a tandem Diels-Alder/ene reaction. The adduct from tiglic aldehyde was converted into isoligularone by conversion to a furan followed by benzylic oxidation.     

Dye-sensitized solar cells based on composite solid polymer electrolytes

The ionic conductivity of polymer electrolytes and their interfacial contact with dye-attached TiO2 particles were enhanced markedly by the addition of amorphous oligomer into polymer electrolytes, resulting in very high overall energy conversion efficiency.     

On the mechanism of reorientational and structural relaxation in supercooled liquids: the role of border dynamics and cooperativity

Molecular dynamics simulation and analysis based upon the many-body potential energy landscape (PEL) are employed to characterize single molecule reorientation and structural relaxation, and their interrelation, in deeply supercooled liquid CS(2). The rotational mechanism changes from small-step Debye diffusion to sudden large angle reorientation (SLAR) as the temperature falls below the mode-coupling temperature T(c). The onset of SLAR is explained in terms of the PEL; it is an essential feature of low-T rotational dynamics, along with the related phenomena of dynamic heterogeneity and the bifurcation of slow and fast relaxation processes. A long trajectory in which the system is initially trapped in a low energy local minimum, and eventually escapes, is followed in detail, both on the PEL and in real space. During the trapped period, "return" dynamics occurs, always leading back to the trap. Structural relaxation is identified with irreversible escape to a new trap. These processes lead to weak and strong SLAR, respectively; strong SLAR is a clear signal of structural relaxation. Return dynamics involves small groups of two to four molecules, while a string-like structure composed of all the active groups participates in the escape. It is proposed that, rather than simple, nearly instantaneous, one-dimensional barrier crossings, relaxation involves activation of the system to the complex, multidimensional region on the borders of the basins of attraction of the minima for an extended period.