Natural Product-Derived Chiral Pyrrolidine-2,5-diones, Their Molecular Structures and Conversion to Pharmacologically Important Skeletons.

The versatility of the natural products (2S,3S)- and (2S,3R)-3-hydroxy-5-oxotetrahydrofuran-2,3-dicarboxylic acids (1 and 2), isolated in large amounts from tropical plant sources, has been demonstrated by the construction of 3-substituted and 3,4-disubstituted chiral pyrrolidine-2,5-diones. The absolute configurations of chiral pyrrolidine-2,5-diones have been ascertained using chiroptical spectroscopic methods and/or single-crystal XRD data. A combination of different reaction strategies delivering a diverse matrix of fused heterocyclic ring systems is presented. The pyrrolo[2,1-a]isoquinoline alkaloid (+)-crispine A possesses a wide range of pharmacological activities including antidepressant, antiplatelet, antileukemic, and anticancer activities. The analogues of indolizino[8,7-b]indole alkaloids (+)- and (-)-harmicine show strong antileishmanial, antinociceptive, PDE5-inhibitory, antimalarial, and antiviral activities. The bicyclic furo[2,3-b]pyrrolo skeleton is present in many natural products. Thus, the uniqueness of relatively cheap, naturally occurring chiral 2-hydroxycitric acid lactones as chirons has been demonstrated by the construction of some important molecular skeletons that are otherwise difficult to synthesize.

Chiroptical spectroscopy of natural products: avoiding the aggregation effects of chiral carboxylic acids.

Determination of the absolute configurations and predominant conformations of chiral natural products, occurring as carboxylic acids, using chiroptical spectroscopic methods becomes challenging due to the formation of solute aggregates (in the form of dimers, etc.) and/or solute-solvent complexes resulting from intermolecular hydrogen bonding with solvent. A hypothesis that such aggregation effects can be avoided by using corresponding sodium salts or acid anhydrides for chiroptical spectroscopic measurements has been tested. For this purpose, vibrational circular dichroism, electronic circular dichroism, and optical rotatory dispersion spectra for disodium salts of two natural products, hibiscus acid and garcinia acid, and the anhydride of acetylated garcinia acid have been measured. These experimental spectra are analyzed in combination with quantum chemical calculations of corresponding spectra. The spectral analysis for sodium salts and anhydride turned out to be simpler, suggesting that the conversion of carboxylic acids to corresponding salts or anhydride can be advantageous for the application of chiroptical spectroscopy.

Chromium-zinc ferrite nanocomposites for the catalytic abatement of toxic environmental pollutants under ambient conditions.

Catalytic abatement of 4-chlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid in water was investigated by peroxide oxidation over chromium substituted zinc ferrite nanocomposites at ambient conditions. The structural and chemical properties of composites synthesized by sol-gel auto combustion method was studied by X-ray diffraction, Fourier Transform Infra-Red spectroscopy, Transmission Electron Microscopy, surface area, X-ray Fluorescence spectroscopy, Temperature Programmed Reduction and Desorption techniques. Complete removal of 4-CP, DCP and 2,4-D was achieved within 60, 75 and 90min with 96.7/90.5%, 93.88/77.23% and 88.55/62.1% of COD/TOC removal respectively at 298K and 343K. Influence of reaction variables including reaction temperature, oxidant concentration, substrate concentration, catalyst dosage and its composition on the removal efficiency was studied. Kinetic study revealed that wet peroxide oxidation followed a first order kinetic model with rate constant and activation energy of 3.5×10-2min-1/10.7kJ/mole, 9.5×10-3min-1/12.9kJ/mole and 2.29×10-2min-1/17.7kJ/mole respectively for 4-CP, DCP and 2,4-D. The results of five consecutive catalytic runs from X-ray diffraction, Brunauer Emmet Teller surface area and leaching studies from Atomic Absorption Spectrophotometry (AAS) revealed the excellent stability of the catalyst. Scavenging effect of n-butanol on hydroxyl radical indicated a heterogeneous free radical mechanism.

Recurrent meningitis due to epidermoid.

Aseptic meningitis is characterized by noninfective serous inflammation of the meninges. It can occur in a recurrent fashion when associated with dermoid and epidermoid cysts due to rupture of cyst contents into subarachnoid space resulting in aseptic chemical meningitis. Bacterial meningitis in association with these tumors is commonly related to a coexisting dermal sinus tract and the most common organism is Staphylococcus aureus.