A total synthesis of the epoxyquinone based antifungal natural product (±)-ambuic acid

A total synthesis of the recently isolated polyketide natural product (+/-)-ambuic acid has been accomplished from the readily available Diels-Alder adduct of cyclopentadiene and 2-allyl-p-benzoquinone through a simple sequence with sound stereocontrol. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of static deflection on natural frequency of non-linear spring mass system by direct linearization method

An exact expression for the frequency of a non-linear cubic spring mass system is obtained considering the effect of static deflection. An alternative expression for the approximate frequency is also obtained by the direct linearization procedure; it is shown that this is very accurate as compared with the exact method. This approximate frequency equation is used to explain a “dual behaviour” of the frequency amplitude curves.

Ion Transport in a Polymer-Plastic Solid Soft Matter Electrolyte in the Light of Solvent Dynamics and Ion Association

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.

Photocytotoxic Lanthanum(III) and Gadolinium(III) Complexes of Phenanthroline Bases Showing Light-Induced DNA Cleavage Activity

Lanthanide complexes of formulation [La(B)(2)(NO3)(3)] (1-3) and [Gd(B)(2)(NO3)(3)] (4-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 4),dipyrido[3,2-d2',3'-f]quinoxaline (dpq in 2,5) and dipyrido[3,2-a2',3'-c]phenazine (dppz in 3, 6), have been prepared, characterized from physicochemical data, and their photoinduced DNA and protein cleavage activity studied The photocytotoxicity of the dppz complexes 3 and 6 has been studied using HeLa cancer cells. The complexes exhibitligand centered bands in the UV region The dppz complexes show thelowest energy band at 380 nm in N,N-dimethylformamide (DMF) The La(III)complexes are diamagnetic. The Gd(III) complexes (4-6) have magneticmoments that correspond to seven unpaired electrons The complexes are1(.)1 electrolytic in aqueous DMF The dpq and dppz complexes in DMFshow ligand-based reductions. The complexes display moderate binding propensity to calf thymus DNA giving binding constant values in the range of 5.7 x 10(4)-5.8 x 10(5) M-1 with a relative order. 3, 6 (dppz)> 2, 5 (dpq) > 1, 4 (phen) The binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes do not show any hydrolytic cleavage of plasmid supercoiled pUC19 DNA. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form onexposure to UV-A light of 365 nm at nanomolar complex concentration. Mechanistic studies reveal the involvement of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) as the cleavage active species.The complexes show binding propensity to bovine serum albumin (BSA)protein giving K-BSA values of similar to 10(5) M-1. The dppz complexes 3 and 6 show BSA protein cleavage activity in UV-A light of 365 nm The dppz complexes 3 and 6 exhibit significant photocytotoxicity in HeLa cells giving respective IC50 values of 341 nM and 573 nM in UV-A light of 365 nm for an exposure time of 15 min (IC50 > 100 mu M in dark for both the complexes) Control experiments show significant dark and phototoxicity of the dppz base alone (IC50 = 413 nM in light with 4 h incubation in dark and 116 mu M in dark with 24 h incubation). A significant decrease in the dark toxicity of the dppz base is observedon binding to the lanthanide ions while retaining similar phototoxicity.

Influence of External Light Waves on the Thermoelectric Power Under Strong Magnetic Field in Ultrathin Films, Quantum Wires and Quantum Dots of Optoelectronic Materials

In this paper, an attempt is made to study the influence of external light waves on the thermoelectric power under strong magnetic field (TPSM) in ultrathin films (UFs), quantum wires (QWs) and quantum dots (QDs) of optoelectronic materials whose unperturbed dispersion relation of the conduction electrons are defined by three and two band models of Kane together with parabolic energy bands on the basis of newly formulated electron dispersion laws in each case. We have plotted the TPSM as functions of film thickness, electron concentration, light intensity and wavelength for UFs, QWs and ODs of InSb, GaAs, Hg1-xCdxTe and In1-xGaxAsyP1-y respectively. It appears from the figures that for UFs, the TPSM increases with increasing thickness in quantum steps, decreases with increasing electron degeneracy exhibiting entirely different types of oscillations and changes with both light intensity and wavelength and these two latter types of plots are the direct signature of light waves on opto-TPSM. For QWs, the opto-TPSM exhibits rectangular oscillations with increasing thickness and shows enhanced spiky oscillations with electron concentration per unit length. For QDs, the opto-TPSM increases with increasing film thickness exhibiting trapezoidal variations which occurs during quantum jumps and the length and breadth of the trapezoids are totally dependent on energy band constants. Under the condition of non-degeneracy, the results of opto-TPSM gets simplified into the well-known form of classical TPSM equation which the function of three constants only and being invariant of the signature of band structure.

Ferrolysis induced soil transformation by natural drainage in Vertisols of sub-humid South India

In sub-humid South India, recent studies have shown that black soil areas (Vertisols and vertic Intergrades), located on flat valley bottoms, have been rejuvenated through the incision of streambeds, inducing changes in the pedoclimate and soil transformation. Joint pedological, geochemical and geophysical investigations were performed in order to better understand the ongoing processes and their contribution to the chemistry of local rivers. The seasonal rainfall causes cycles of oxidation and reduction in a perched watertable at the base of the black soil, while the reduced solutions are exported through a loamy sand network. This framework favours a ferrolysis process, which causes low base saturation and protonation of clay, leading to the weathering of 2:1 then 1:1 clay minerals. Maximum weathering conditions occur at the very end of the wet season, just before disappearance of the perched watertable. Therefore, the by-products of soil transformation are partially drained off and calcareous nodules, then further downslope, amorphous silica precipitate upon soil dehydration. The ferrolysed area is fringing the drainage system indicating that its development has been induced by the streambed incision. The distribution of C-14 ages of CaCO3 nodules suggests that the ferrolysis process started during the late Holocene, only about 2 kyr B.P. at the studied site and about 5 kyr B.P. at the watershed outlet. The results of this study are applied to an assessment of the physical erosion rate (4.8x10(-3) m/kyr) since the recent reactivation of the erosion process. (C) 2010 Elsevier B.V. All rights reserved.

Natural frequencies and modes of tapered skew plates

The vibration of simply supported skew plates having a linear variation in thickness in one direction is considered. Approximate analysis is made by using Lagrange's equations employing the double Fourier sine series in oblique co-ordinates to represent the deflected surface. Natural frequencies are obtained for rhombic plates for several ranges of thickness variation and skew angle. The nodal patterns plotted for a few typical configurations show interesting metamorphoses with variation in thickness and skew angle.

Evolution, Homology Conservation, and Identification of Unique Sequence Signatures in GH19 Family Chitinases

The discovery of GH (Glycoside Hydrolase) 19 chitinases in Streptomyces sp. raises the possibility of the presence of these proteins in other bacterial species, since they were initially thought to be confined to higher plants. The present study mainly concentrates on the phylogenetic distribution and homology conservation in GH19 family chitinases. Extensive database searches are performed to identify the presence of GH19 family chitinases in the three major super kingdoms of life. Multiple sequence alignment of all the identified GH19 chitinase family members resulted in the identification of globally conserved residues. We further identified conserved sequence motifs across the major sub groups within the family. Estimation of evolutionary distance between the various bacterial and plant chitinases are carried out to better understand the pattern of evolution. Our study also supports the horizontal gene transfer theory, which states that GH19 chitinase genes are transferred from higher plants to bacteria. Further, the present study sheds light on the phylogenetic distribution and identifies unique sequence signatures that define GH19 chitinase family of proteins. The identified motifs could be used as markers to delineate uncharacterized GH19 family chitinases. The estimation of evolutionary distance between chitinase identified in plants and bacteria shows that the flowering plants are more related to chitinase in actinobacteria than that of identified in purple bacteria. We propose a model to elucidate the natural history of GH19 family chitinases.

Steroids and related natural products. VIII. Synthesis of oxasteroids

Peroxydisulfuric acid oxidation of testosterone propionate, progesterone, and cholest-4-en-3-one has been shown to yield 3-oxo-17β-hydroxy-4-oxa-5α-androstane (I, after saponification), 3,20-dioxo-4-oxa-5α-pregnane (V) and 3-oxo-4-oxa-5α-cholestane (VII) respectively. Boron trifluoride etherate-lithium aluminum hydride reduction of δ-lactones I, V, and VII led to the corresponding tetrahydropyran derivatives (IIb, VIa, and VIII). Similar reduction of 3β-hydroxy-17-oxo-17a-oxa-D-homo-5α-androstane (XI) gave 3β-hydroxy-17a-oxa-D-homo-5α-androstane (XIIa). Diborane-boron trifluoride etherate was also found to reduce lactones to cyclic ethers, while reduction with diborane gave hemiacetals. Evidence in support of the structures and stereochemistry assigned to the lactones and their unusual reduction products has been summarized. A tentative mechanism is proposed for lactone → ether reduction employing diborane-boron trifluoride etherate.

Steroids and related natural products. VII. Boron trifluoride etherate-lithium aluminum hydride reduction of smilagenin acetate

Reduction of smilagenin acetate (Va) using a boron trifluoride etherate-lithium aluminum hydride reagent, followed by hydrogen peroxide oxidation and acetylation, was found to yield: 3β-ethoxysmilagenin (Vb), 3β-ethoxydihydrosmilagenin acetate (VIa), dihydrosmilagenin diacetate (VIb), and a complex mixture of partially acetylated products. Similar reaction conditions were employed to convert dihydrodiosgenin (II) to dihydrochlorogenin (III). Boron trifluoride etherate-lithium aluminum hydride reduction of 3β-acetoxy-5α-cholestane and 3β-acetoxy-5α-lanostane (VIIIa) was shown to yield the corresponding 3β-ethoxy (e.g., VIIIb) derivatives.

Natural history and behaviour of the primitively eusocial wasp Ropalidia marginata (Hymenoptera: Vespidae): a comparison of the two sexes

We report the natural history and behaviour of the primitively eusocial wasp Ropalidia marginata with a special reference to the males. We found that just as nests of this species are found throughout the year, so are the males. Females spend all their life in their nests but males stay in their natal nests only for 1-12 days and leave to lead a nomadic life. Males maintained in the laboratory can live for up to 140 days. Like all eusocial hymenopteran males, R. marginata males also do not perform any colony maintenance activities. We found that males did not forage or feed larvae. Compared with females, males showed fewer dominance and subordinate behaviours and being solicited behaviour and more feeding self and soliciting behaviours. By comparing males with young females, we found similar differences, except that the males showed similar rates of feeding self and higher rates of subordinate behaviour.

Phonon-mediated two-magnon light scattering from ferromagnetic insulators

An indirect mechanism of light scattering from spin-waves in ferromagnetic insulators via two-magnon one-phonon process is proposed. Following linear response theory, an expression has been derived for the differential scattering cross-section in the mean-field-approximation.

Natural modes of a coupled non-linear system

The natural modes of a non-linear system with two degrees of freedom are investigated. The system, which may contain either hard or soft springs, is shown to possess three modes of vibration one of which does not have any counterpart in the linear theory. The stability analysis indicates the existence of seven different modal stability patterns depending on the values of two parameters of non-linearity.

On Using Projective Relations for Calibration and Estimation in a Structured-Light Scanner

For structured-light scanners, the projective geometry between a projector-camera pair is identical to that of a camera-camera pair. Consequently, in conjunction with calibration, a variety of geometric relations are available for three-dimensional Euclidean reconstruction. In this paper, we use projector-camera epipolar properties and the projective invariance of the cross-ratio to solve for 3D geometry. A key contribution of our approach is the use of homographies induced by reference planes, along with a calibrated camera, resulting in a simple parametric representation for projector and system calibration. Compared to existing solutions that require an elaborate calibration process, our method is simple while ensuring geometric consistency. Our formulation using the invariance of the cross-ratio is also extensible to multiple estimates of 3D geometry that can be analysed in a statistical sense. The performance of our system is demonstrated on some cultural artifacts and geometric surfaces.