Radical Annulation Strategy to Chiral Pupukeanones: Total Synthesis of (+)-10-ex&l(- Naphthyl)pupukean-9-onea nd (+)-lO-exo-l(- Naphthyl)-5-epipupukean-9-ones1

Intramolecular alkylation reaction of the bromoenone 12, obtained from S-carvone in three steps, furnished the bicyclo[2.2.2]octenone 13. Contrary to the anticipated radical annulation reaction, the bicyclic bromides 14 and 15, obtained from the enone 13, generated exclusively the cyclopropane product 18 via a 3-exo-trig radical cyclization on reaction with nBu3SnH and AIBN, even in the presence of a large excess of a radicophile. On the other hand, bromoenone 24, synthesized from R-carvone via S-naphthylcarvone 21, underwent radical annulation reaction in the presence of radicophiles to furnish the isotwistanes 25-28 in a regio- and stereospecific manner. Hydrogenation of the olefin 34, obtained from the diketone 27 via a regiospecific Wittig reaction, furnished the naphthyl-5-epipupukean-9-one 33, whereas stereoselective hydrogenation of the enone 36, prepared from the keto ester 25 via a Grignard reaction and dehydration sequence, generated the naphthylpupukeanone 32.

Squeezed states, photon-number distributions, and U(l) invariance

We study the photon-number distribution in squeezed states of a single-mode radiation field. A U(l)-invariant squeezing criterion is compared and contrasted with a more restrictive criterion, with the help of suggestive geometric representations. The U(l) invariance of the photon-number distribution in a squeezed coherent state, with arbitrary complex squeeze and displacement parameters, is explicitly demonstrated. The behavior of the photon-number distribution for a representative value of the displacement and various values of the squeeze parameter is numerically investigated. A new kind of giant oscillation riding as an envelope over more rapid oscillations in this distribution is demonstrated.

Stereochemical properties and x-ray structure of a water-soluble diastereomeric (arene)ruthenium(II) Schiff-base complex: [Ru(.eta.-MeC6H4Pri-p)(H2O)(L*)](ClO4), containing a weakly bound aqua ligand [HL* = (S)-(.alpha.-methylbenzyl)salicylaldimine]

An air-stable and water-soluble diastereomeric half-sandwich ruthenium(I1) complex, [Ru(s-MeCsH4Pr'-p)(H*O)-(L*)] (C104) (l), has been isolated and structurally characterized [HL* = (27)-(a methylbenzyl)salicylaldimine,2-HOC6H4CH-NCHMePhI. Complex 1, Czd-I3oNO&lRu, crystallizes in the noncentric triclinic space group P1 with a = 9.885(1) A, b = 10.185(1) A, c = 14.187(2) A, a = 110.32(1)', 6 = 102.17(1)', y = 102.41(1)O, V=1243( 1) A3, and 2 = 2. The X-ray structure shows the presence of two diastereomers in a 1:l ratio having RR,,,SCand SR,,,&c onfigurations. The Ru-OHz bond distances are considerably long, and the values for RR, - a~n d SRu-1isomers are 2.1 19(5) and 2.203(5) A, respectively. The aqua complex (1) exists as a single diastereomer in solution,and it forms stable adducts with P-, N-, and halide-donor ligands. The stereochemical changes associated with adduct-forming reactions follow an inversion order: PPhs >> P(OMe)3 > pyridine bases >> halides (I, Br, Cl) >H20.

A regiospecific radical annulation strategy to functionalised chiral bicyclo[3.3.l]nonanes

A radical annulation, i.e. an intermolecular radical Michael addition followed by an intramolecular Michael addition of the resultant radical (radical cyclisation) has been employed for the construction of chiral functionalised bicyclo[3.3,1]-nonanes. Thus reaction of carvone hydrohalides 7 with (n)Bu(3)SnH and AIBN in the presence of excess of radicophiles 4 furnished, regiospecifically bicyclo[3.3.1]nonanes 8-14, introducing three new chiral centres in a stereoselective manner. Analogously the bromide 18 generated the bridgehead substituted bicyclo[3.3.1]-nonanes 19-21.

Chloroplastic glutamine synthetase from normal and water stressed safflower (Carthamus tinctorius L.) leaves

The chloroplastic isoform of glutamine synthetase (GS(2), EC 6.3.1.2) from normal and water stressed safflower (Carthamus tinctorius L. cv.A-300) leaves has been purified to apparent electrophoretic homogeneity by a procedure involving anion-exchange, hydrophobic and size-exclusion chromatography followed by electroelution of the protein from preparative polyacrylamide gels. The observed molecular weight of the native protein varied from 305-330 kDa depending on the sizing column employed. The native protein is composed of 44 kDa subunits. Under conditions of saturating ammonium and at ATP levels of 0.1-10 mM, double-reciprocal plots with respect to glutamate are biphasic and concave downward at high concentrations of the varied substrate for normal enzyme but are linear for enzyme from water-stressed plants. Under subsaturating ATP levels, K-Glu is over 18-fold lower for enzyme from stressed leaves. The K-m, (ATP) varies with Mg2+ levels in the assay mixture. Double-reciprocal plots of initial velocity with respect to ATP at changing fixed levels of NH4+ are linear for normal enzyme but are curved upwards for enzyme from stressed leaves. Initial velocity data of 1/v vs. 1/ammonium for the enzyme from both the sources are non-linear (curved upwards) when ATP is saturating. At subsaturating ATP levels, the data are linear for normal enzyme but are still non-linear for the enzyme from stressed leaves. The results obtained suggest positively cooperative binding of NH4+ A V-max(/2) value of 3.6 mM for Mg2+ was obtained at 5 mM ATP. The isoelectric point of the native protein from normal and stressed leaves was determined to be, respectively, 5.6 and 6.1. The mixed competitive and competitive inhibitors, methionine sulfoximine and ADP and K-i values of 0.086 mM (0.017 for the enzyme from stressed leaves) and 2.15 mM (1.70 for the enzyme from stressed leaves), respectively. Enzyme from stressed leaves is not inhibited by 5 mM proline. The observed kinetic constants of GS(2) from normal and water stressed safflower seedlings are discussed in relation to the known water-stress tolerance of this crop plant.

Interaction of EcoP1 modification methylase with S-adenosyl-L-methionine: a UV-crosslinking study

EcoP1 modification methylase was radioactively labeled when incubated with S-adenosyl-L-[methyl-3H]methionine in the presence of ultraviolet light. Crosslinking of the enzyme as detected by electrophoresis on sodium dodecyl sulfate-polyacrylamide gel followed by fluorography and autoradiography, was shown to be specific by a number of criteria. More importantly, EcoP1 modification methylase was also radioactively labeled with S-adenosyl-L-[carboxyl-14C]methionine demonstrating that labeling involved binding of the entire AdoMet molecule rather than methylation of the protein. Further, c2 EcoP1 mutant DNA modification methylases which show negligible or very little methylation activity, correspondingly formed a weak or no adduct upon crosslinking. These results suggest that photolabeling of EcoP1 DNA modification methylase occurs at the AdoMet binding site.

Interactions of L-serine at the active site of serine hydroxymethyltransferases: induction of thermal stability

Serine hydroxymethyltransferase (SHMT), EC 2.1.2.1, exhibits broad substrate and reaction specificity. In addition to cleaving many 3-hydroxyamino acids to glycine and an aldehyde, the enzyme also catalyzed the decarboxylation, transamination and racemization of several substrate analogues of amino acids. To elucidate the mechanism of interaction of substrates, especially L-serine with the enzyme, a comparative study of interaction of L-serine with the enzyme from sheep liver and Escherichia coli, was carried out. The heat stability of both the enzymes was enhanced in the presence of serine, although to different extents. Thermal denaturation monitored by spectral changes indicated an alteration in the apparent T, of sheep liver and E. coli SHMTs from 55 +/- 1 degrees C to 72 +/- 3 degrees C at 40 mM serine and from 67 +/- 1 degrees C to 72 +/- 1 degrees C at 20 mM serine, respectively. Using stopped flow spectrophotometry k values of (49 +/- 5)(.)10(-3) s(-1) and (69 +/- 7).10(-3) s(-1) for sheep liver and E. coli enzymes were determined at 50 mM serine. The binding of serine monitored by intrinsic fluorescence and sedimentation velocity measurements indicated that there was no generalized change in the structure of both proteins. However, visible CD measurements indicated a change in the asymmetric environment of pyridoxal 5'-phosphate at the active site upon binding of serine to both the enzymes. The formation of an external aldimine was accompanied by a change in the secondary structure of the enzymes monitored by far UV-CD spectra. Titration microcalorimetric studies in the presence of serine (8 mM) also demonstrated a single class of binding and the conformational changes accompanying the binding of serine to the enzyme resulted in a more compact structure leading to increased thermal stability of the enzyme.

Peanut agglutinin from callus and cell suspension cultures of Arachis hypogaea L

Synthesis of peanut agglutinin was induced in callus and cell suspension cultures of cotyledons of peanut (Arachis hypogaea L.). The lectin was synthesised in cultures through several passages. Biosynthesis of peanut agglutinin was regulated by the type and concentration of exogenous growth regulators and was positively correlated to the growth of the cultures,indicating that the agglutinin may have a role to play during cell growth. Movement of agglutinin from the cells into the medium not only facilitated easy isolation of the lectin but also provided a clue that it may probably serve as a defence molecule. The synthesized lectin purified from culture, was found to be biologically active, and was found to be comparable with the lectin from seeds, in terms of its electrophoretic mobility.

Photolabeling of the EcoP15 DNA methyltransferase with S-adenosyl-l-methionine

Radioactivity from S-adenosyl-L-[methyl-H-3] methionine ([methyl-H-3]AdoMet) was bound to the EcoP15 DNA methyltransferase (M.EcoP15) following short-wave ultraviolet (UV) irradiation. The labeled protein was subjected to polyacrylamide-gel electrophoresis in the presence of sodium dodecyl sulfate (SDS-PAGE), and detected by fluorography and autoradiography. Labeling was found to be dependent on the concentration of AdoMet and time of UV irradiation. The photolabeling by [methyl-H-3]AdoMet was specific and blocked by S-adenosyl-L-homocysteine (AdoHcy) and sinefungin which are known to function as competitive inhibitors. Limited digestion of the M EcoP15-AdoMet adduct by Staphylococcus aureus protease V8 generated three peptides of approx. 50, 32 and 30 kDa; Interestingly, only the 30-kDa peptide fragment contained radioactivity, as detected by SDS-PAGE, followed by fluorography and autoradiography. Further, sequencing of a few amino acids at the N-terminus of these peptides showed that the 30-kDa fragment was the N-terminal portion of M.EcoP15, These results suggest that photolabeling is at the AdoMet-binding site and that the N-terminal half of M.EcoP15 may be involved in substrate binding.

Use of L matrix to obtain reliable ab initio force constants of polyatomic molecules: ethylene as a test system

Direct use of experimental eigenvalues of the vibrational secular equation on to the ab initio predicted eigenvector space is suggested as a means of obtaining a reliable set of intramolecular force constants. This method which we have termed RECOVES (recovery in the eigenvector space) is computationally simple and free from arbitrariness. The RECOVES force constants, by definition, reproduce the experimental vibrational frequencies of the parent molecule exactly. The ab initio calculations were carried out for ethylene as a test molecule and the force constants obtained by the present procedure also correctly predict the vibrational frequencies of the deuterated species. The RECOVES force constants for ethylene are compared with those obtained by using the SQM procedure.

Photochemistry of benzylidene-d,l-piperitones in solution and the melt phase

The solution- and melt-phase photochemistry of four trans-benzylidene-d,l-piperitones (1) has been investigated under a variety of conditions. The 1 undergo trans reversible cis isomerization to establish a quasi photostationary state. Further irradiation leads to 2 via oxidative ring closure. Conspicuously absent are dimers (obtained upon irradiation of the neat crystals) and the plausible Norrish Type II photoproducts, 3. Although 1c yields 2c, no evidence for the alternative cyclization route to 2a (requiring loss of HCl) has been observed. Rationalizations for the transformations are presented. The structure of 2b has been determined unambiguously from X-ray crystallographic analysis.

Plantlet production from shoot tip cultures of red sandalwood ( Pterocarpus santalinus L.)

Red sandalwood (Pterocarpus santalinus L.), belonging to the family Fabaceae, is one of the most valuable trees, and has limited distribution in India. In view of its high price, restricted distribution and usefulness as a timber tree, there is urgent need to obtain improved lines, in both quality and quantity. We have established a method for production of complete plantlets by tissue culture. We report here the successful development of red sandalwood plantlets by induction of multiple shoots from shoot tips, and successful transfer of micropropagated plants to soil.

The mean and turbulence structure simulation of the monsoon trough boundary layer using a one-dimensional model with e-l and e-epsilon closures

An attempt has been made here to study the sensitivity of the mean and the turbulence structure of the monsoon trough boundary layer to the choice of the constants in the dissipation equation for two stations Delhi and Calcutta, using one-dimensional atmospheric boundary layer model with e-epsilon turbulence closure. An analytical discussion of the problems associated with the constants of the dissipation equation is presented. It is shown here that the choice of the constants in the dissipation equation is quite crucial and the turbulence structure is very sensitive to these constants. The modification of the dissipation equation adopted by earlier studies, that is, approximating the Tke generation (due to shear and buoyancy production) in the epsilon-equation by max (shear production, shear + buoyancy production), can be avoided by a suitable choice of the constants suggested here. The observed turbulence structure is better simulated with these constants. The turbulence structure simulation with the constants recommended by Aupoix et al (1989) (which are interactive in time) for the monsoon region is shown to be qualitatively similar to the simulation obtained with the constants suggested here, thus implying that no universal constants exist to regulate dissipation rate. Simulations of the mean structure show little sensitivity to the type of the closure parameterization between e-l and e-epsilon closures. However the turbulence structure simulation with e-epsilon closure is far better compared to the e-l model simulations. The model simulations of temperature profiles compare quite well with the observations whenever the boundary layer is well mixed (neutral) or unstable. However the models are not able to simulate the nocturnal boundary layer (stable) temperature profiles. Moisture profiles are simulated reasonably better. With one-dimensional models, capturing observed wind variations is not up to the mark.

The fatigue crack growth rate in L-72 Al-alloy plate specimens with cold worked holes

A fatigue crack growth rate study has been carried out on L-72 aluminium alloy plate specimens with and without cold worked holes. The cold worked specimens showed significantly increased fatigue life compared to unworked specimens. Computer software is developed to evaluate the stress intensity factor for non-uniform stress distributions using Green's function approach. The exponents for the Paris equation in the stable crack growth region for cold worked and unworked specimens are 1.26 and 3.15 respectively. The reduction in exponent value indicates the retardation in crack growth rate. An SEM study indicates more plastic deformation at the edge of the hole for unworked samples as compared to the worked samples during the crack initiation period.

Hydrogen-Bond-Directed Nonlinear-Optical Organic Materials - Evidence For The Control Of 2nd-Harmonic Generation Activities From The X-Ray Crystal-Structures Of The Complexes Of L-Tartaric Acid With M-Anisidine and P-Toluidine

Several substituted anilines were converted to binary salts with L-tartaric acid. Second harmonic generation (SHG) activities of these salts were determined. The crystal packing in two structures, (i) m-anisidinium-L-tartrate monohydrate (i) and (ii) p-toluidinium-L-tartrate (2), studied using X-ray diffraction demonstrates that extensive hydrogen bonding steers the components into a framework which has a direct bearing on the SHG activity