A new flavanoid from the flowers of Azadirachta indica

Studies on the chemical constituents of the flowers of Azadirachta indica have led to the isolation of one new flavanone named as azharone (5,7,4'-trihydroxy-3'-(3'-methyl-2',3'-epoxybutyl)flavan-4-one (3)) along with two known constituents azadirone (1), and isoazadironolide (2). Their structures have been elucidated through spectral studies including 2D-NMR (COSY-45, NOESY, J-resolved, HMQC, HMBC) experiments.     

Crystal structures and catalytic mechanism of the Arabidopsis cinnamyl alcohol dehydrogenases AtCAD5 and AtCAD4

The cinnamyl alcohol dehydrogenase (CAD) multigene family in planta encodes proteins catalyzing the reductions of various phenylpropenyl aldehyde derivatives in a substrate versatile manner, and whose metabolic products are the precursors of structural lignins, health-related lignans, and various other metabolites. In Arabidopsis thaliana, the two isoforms, AtCAD5 and AtCAD4, are the catalytically most active being viewed as mainly involved in the formation of guaiacyl/syringyl lignins. In this study, we determined the crystal structures of AtCAD5 in the apo-form and as a binary complex with NADP+, respectively, and modeled that of AtCAD4. Both AtCAD5 and AtCAD4 are dimers with two zinc ions per subunit and belong to the Zn-dependent medium chain dehydrogenase/reductase (MDR) superfamily, on the basis of their overall 2-domain structures and distribution of secondary structural elements. The catalytic Zn2+ ions in both enzymes are tetrahedrally coordinated, but differ from those in horse liver alcohol dehydrogenase since the carboxyl side-chain of Glu70 is ligated to Zn2+ instead of water. Using AtCAD5, site-directed mutagenesis of Glu70 to alanine resulted in loss of catalytic activity, thereby indicating that perturbation of the Zn2+ coordination was sufficient to abolish catalytic activity. The substrate-binding pockets of both AtCAD5 and AtCAD4 were also examined, and found to be significantly different and smaller compared to that of a putative aspen sinapyl alcohol dehydrogenase (SAD) and a putative yeast CAD. While the physiological roles of the aspen SAD and the yeast CAD are uncertain, they nevertheless have a high similarity in the overall 3D structures to AtCAD5 and 4. With the bona fide CAD's from various species, nine out of the twelve residues which constitute the proposed substrate-binding pocket were, however, conserved. This is provisionally considered as indicative of a characteristic fingerprint for the CAD family.     

Secoisolariciresinol dehydrogenase: mode of catalysis and stereospecificity of hydride transfer in Podophyllum peltatum

Secoisolariciresinol dehydrogenase (SDH) catalyzes the NAD+ dependent enantiospecific conversion of secoisolariciresinol into matairesinol. In Podophyllum species, (-)-matairesinol is metabolized into the antiviral compound, podophyllotoxin, which can be semi-synthetically converted into the anticancer agents, etoposide, teniposide and Etopophos. Matairesinol is also a precursor of the cancer-preventative "mammalian" lignan, enterolactone, formed in the gut following ingestion of, for example, various high fiber dietary foods, as well as being an intermediate to numerous defense compounds in vascular plants. This study investigated the mode of enantiospecific Podophyllum SDH catalysis, the order of binding, and the stereospecificity of hydride abstraction/transfer from secoisolariciresinol to NAD+. SDH contains a highly conserved catalytic triad (Ser153, Tyr167 and Lys171), whose activity was abolished with site-directed mutagenesis of Tyr167Ala and Lys171Ala, whereas mutagenesis of Ser153Ala only resulted in a much reduced catalytic activity. Isothermal titration calorimetry measurements indicated that NAD+ binds first followed by the substrate, (-)-secoisolariciresinol. Additionally, for hydride transfer, the incoming hydride abstracted from the substrate takes up the pro-S position in the NADH formed. Taken together, a catalytic mechanism for the overall enantiospecific conversion of (-)-secoisolariciresinol into (-)-matairesinol is proposed.     

Analytical Approach to Space- and Time-Fractional Burgers Equations

A scheme is developed to study numerical solution of the space- and time-fractional Burgers equations under initial conditions by the homotopy analysis method. The fractional derivatives are considered in the Caputo sense. The solutions are given in the form of series with easily computable terms. Numerical solutions are calculated for the fractional Burgers equation to show the nature of solution as the fractional derivative parameter is changed.     

Precision continuous-wave cavity ringdown spectroscopy of CO<Subscript>2</Subscript> at 1064 nm

A high performance continuous-wave cavity ringdown spectrometer using a rapidly swept cavity has been applied to investigate weak absorption of CO₂ line near 1064 nm. In the experimental setup, offset locking of the Nd:YAG laser to other iodine-stabilized Nd:YAG laser provides a frequency accuracy better than 20 kHz. The ringdown time was obtained by fitting the experimental ringdown data to a theoretically obtained ringdown curve. The absorption coefficient and absolute center wavelength are determined with accuracy better than two orders of magnitude with respect to the previous observations. Our experimental setup yields high performance in a relatively simple, low cost, and compact system that is amenable to chemical analysis of trace gases in medicine, agriculture, industry, and the environment.     

Solvability of a class of boundary value problems in the space of convergent sequences

We consider two types of infinite systems of second-order differential equations with boundary conditions in the Banach sequence space c. For each system, sufficient conditions are provided for the existence of solutions. Our approach is based on the use of measure of noncompactness concept and the application of Darbo’s theorem for condensing operators. Some examples are presented to illustrate the obtained results.     

Transfer of radioactivity from soil to vegetation in Rechna Doab,Pakistan

In Rechna Doab, samples of the most common vegetation, perennial grass Desmostachya bipinnata (dab), were collected along with soil samples from 29 sites. Natural radioactivity of ²²⁶Ra, ²³²Th/²²⁸Ac and ⁴⁰K was measured by using high purity germanium-based gamma ray spectrometer. Activity concentration levels of ²²⁶Ra, ²³²Th/²²⁸Ac and ⁴⁰K in soil were found to be 46.8±6.2 (36.0–57.6), 61.4±5.9 (48.2–73.2) and 644.8±73.9 (537.7–868.4) Bq kg^?1 (dry mass), respectively, and those in vegetation were 2.74±1.70 (1.00–6.39), 2.24±0.59 (1.56–2.61) and 172.72±113.37 (53.14–469.24) Bq kg^?1 (dry mass), respectively. The measured values of the activity concentration in vegetation are comparable with some other international data. Calculated soil to vegetation transfer factors of ²²⁶Ra, ²²⁸Ac and ⁴⁰K were 0.06±0.03 (0.02–0.14), 0.04±0.01 (0.03–0.04) and 0.26±0.16 (0.09–0.69). The mean outdoor absorbed dose rate in air for the area under study was determined as 8.22 nGy h^?1 and the mean indoor absorbed dose rate in air was 11.52 nGy h^?1. The total annual effective dose to the general public from the vegetation was found to be (0.02–0.16) mSv, which is below the recommended limit value of 1 mSv y^?1 for the general public. The dab vegetation under study was found to be radiologically safe for the population and environment.     

Electrochemical Study Of Substituted Polyparaphenylene Derivatives In Aqueous And Organic Medium

In recent years, organic conducting polymers have made concrete inroads in the field of battery materials. In the present communication we report, the synthesis and oxidation potentials of poly-p-phenylene (PPP) , polymethylphenylene (PPPmethyl), polypropylphenylene (PPPpropyl), polysulphophenylene (PPPS03H), polychlorophenylene (PPPCl), polynitrophenylene (PPPN02) and polyaminophenylene (PPPNHz). A mixture of polyvinylidene fluoride (PVF) and acetylenic carbon was used as conducting adhesive to study electrochemical properties of PPP and derivatives in acetonitrile containing 0.2 M LiCl0₄ and aqueous sulphuric acid media. We discuss the effects of the substituent groups on PPP and possibilities of its use as a battery material in the light of EPR, conductivity and electrochemical results.