Synthesis based on cyclohexadienes .24. A new total synthesis of pupukean-2-one and a facile entry to copa and ylanga type sesquiterpene skeletons

A novel tandem 5-exo-trig allyl and 3-exo-trig radical cyclisation and rearrangement to copa and ylanga type sesquiterpene skeletons from easily prepared cyclohexadienes is reported, A new total synthesis of pupukean-2-one 8, which belongs to a novel class of sesquiterpenes, involving a 5-exo-trig allyl radical cyclisation as the key step is also reported.

Zn incorporation and band gap shrinkage in p-type GaAs

Dimethylzine (DMZn) was used as a p-type dopant in GaAs grown by low pressure metalorganic vapor phase epitaxy using trimethylgallium and arsine (AsH3) as source materials, The hole carrier concentrations and zinc (Zn) incorporation efficiency are studied by using the Hall effect, electrochemical capacitance voltage profiler and photoluminescence (PL) spectroscopy, The influence of growth parameters such as DMZn mole fraction, growth temperature, and AsH, mole fraction on the Zn incorporation have been studied. The hole concentration increases with increasing DMZn and AsH3 mole fraction and decreases with increasing growth temperature. This can be explained by vacancy control model. The PL experiments were carried out as a function of hole concentration (10(17)-1.5 x 10(20) cm(-3)). The main peak shifted to lower energy and the full width at half maximum (FWHM) increases with increasing hole concentrations. We have obtained an empirical relation for FWHM of PL, Delta E(p)(eV) = 1.15 x 10(-8)p(1/3). We also obtained an empirical relation for the band gap shrinkage, Delta E-g in Zn doped GaAs as a function of hole concentration. The value of Delta E-g(eV) = -2.75 x 10(-8)p(1/3), indicates a significant band gap shrinkage at high doping levels, These relations are considered to provide a useful tool to determine the hole concentration in Zn doped GaAs by low temperature PL measurement. The hole concentration increases with increasing AsH3 mole fraction and the main peak is shifted to a lower energy side. This can be explained also by the vacancy control model. As the hole concentration is increased above 3.8 x 10(18) cm(-3), a shoulder peak separated from the main peak was observed in the PL spectra and disappears at higher concentrations. (C) 1997 American Institute of Physics.

Si incorporation and Burstein-Moss shift in n-type GaAs

Silane (SiH4) was used as an n-type dopant in GaAs grown by low pressure metalorganic vapor phase epitaxy using trimethylgallium (TMGa) and arsine (AsH3) as source materials. The electron carrier concentrations and silicon (Si) incorporation efficiency are studied by using Hall effect, electrochemical capacitance voltage profiler and low temperature photoluminescence (LTPL) spectroscopy. The influence of growth parameters, such as SiH4 mole fraction, growth temperature, TMGa and AsH3 mole fractions on the Si incorporation efficiency have been studied. The electron concentration increases with increasing SIH4 mole fraction, growth temperature, and decreases with increasing TMGa and AsH3 mole fractions. The decrease in electron concentration with increasing TMGa can be explained by vacancy control model. The PL experiments were carried out as a function of electron concentration (10(17) - 1.5 x 10(18) cm(-3)). The PL main peak shifts to higher energy and the full width at half maximum (FWHM) increases with increasing electron concentrations. We have obtained an empirical relation for FWHM of PL, Delta E(n) (eV) = 1.4 x 10(-8) n(1/3). We also obtained an empirical relation for the band gap shrinkage, Delta E-g in Si-doped GaAs as a function of electron concentration. The value of Delta E-g (eV) = -2.75 x 10(-8) n(1/3), indicates a significant band gap shrinkage at high doping levels. These relations are considered to provide a useful tool to determine the electron concentration in Si-doped GaAs by low temperature PL measurement. The electron concentration decreases with increasing TMGa and AsH3 mole fractions and the main peak shifts to the lower energy side. The peak shifts towards the lower energy side with increasing TMGa variation can also be explained by vacancy control model. (C) 1999 Elsevier Science S.A. All rights reserved.

Tidally compressed gas in centers of early-type and ultraluminous galaxies

In this paper we propose that the compressive tidal held in the centers of flat-core early-type galaxies and ultraluminous galaxies compresses molecular clouds producing dense gas observed in the centers of these galaxies. The effect of galactic tidal fields is usually considered disruptive in the literature. However, for some galaxies, the mass profile flattens toward the center and the resulting galactic tidal field is not disruptive, but instead it is compressive within the flat-core region. We have used the virial theorem to determine the minimum density of a molecular cloud to be stable and gravitationally bound within the tidally compressive region of a galaxy. We have applied the mechanism to determine the mean molecular cloud densities in the centers of a sample of flat-core, early-type galaxies and ultraluminous galaxies. For early-type galaxies with a core-type luminosity profile, the tidal held of the galaxy is compressive within half the core radius. We have calculated the mean gas densities for molecular gas in a sample of early-type galaxies which have already been detected in CO emission, and we obtain mean densities of [n] similar to 10(3)-10(6) cm(-3) within the central 100 pc radius. We also use our model to calculate the molecular cloud densities in the inner few hundred parsecs of a sample of ultraluminous galaxies. From the observed rotation curves of these galaxies we show that they have a compressive core within their nuclear region. Our model predicts minimum molecular gas densities in the range 10(2)-10(4) cm(-3) in the nuclear gas disks; the smaller values are applicable typically for galaxies with larger core radii. The resulting density values agree well with the observed range. Also, for large core radii, even fairly low-density gas (similar to 10(2) cm(-3)) can remain bound and stable close to the galactic center.

Prevalence of, and antigenic variation in, serotype G10 rotaviruses and detection of serotype G3 strains in diarrheic calves: Implications for the origin of G10P11 or P11 type reassortant asymptomatic strains in newborn children in India

Previous studies have shown predominant association of G10P11 type bovine rotavirus-derived reassortant strains with asymptomatic infections in newborn children in India. To understand the epidemiological and genetic basis for the origin of these strains in humans, the relative frequencies of different serotypes among bovine rotaviruses (BRVs) isolated from southern, western and central regions of the country were determined by subgroup and serotype analysis as well as nucleotide (nt) sequence analysis of the genes encoding the outer capsid proteins VP4 and VP7. Since the human G10P11 asymptomatic neonatal strain I321 possessed NSP1 from a human rotavirus, to determine its genetic origin in the bovine strains, comparative analysis of partial gene sequences from representative G10P11 strains was also carried out. The following observations were of great epidemiological significance, (i) G10P11 strains predominated in all the three regions with frequencies ranging between 55.6% and 85.2%. In contrast to the high prevalence of G6 strains in other countries, only one G6 strain was detected in this study and G8 strains represented 5.8% of the isolates, (ii) among the G10 strains, in serotyping ELISA, four patterns of reactivity were observed that appeared to correlate with the differences in electropherotypic patterns and amino acid (aa) sequence of the VP7, (iii) surprisingly, strains belonging to serotype G3 were detected more frequently (10.7%) than those of serotypes G6 and G8 combined, while strains representing the new serotype (G15) were observed in a single farm in Bangalore, and (iv) about 3.9% of the isolates were nontypeable as they exhibited high cross-reactivity to the serotyping MAbs used in the study. Comparative analysis of the VP7 gene sequence from the prototype G3 MAb-reactive bovine strain J63 revealed greatest sequence relatedness (87.6% nt and 96.0% aa) with that of serotype G3 rhesus-monkey strain RRV. It also exhibited high sequence homology with the VP7 from several animal and animal rotavirus-related human G3 strains (Simian SA11; equine ERV316 and FI-14. canine CU-1 and K9; porcine 4F; Feline Cat2 and human HCR3, YO and AU1). Partial nucleotide sequence analysis of the NSP1 gene of J63 showed greatest nt sequence homology (95.9%) to the NSP1 gene allele of the Indian G8 strain, isolated from a diarrheic child, which is likely to have been transmitted directly from cattle and 92.6% homology to that of the bovine G8 strain A5-10 suggesting the likely origin of J63 by gene reassortment between a bovine G8 strain and a G3 animal strain. Prevalence of G10P11 strains in cattle and G10P11 or P11 type reassortant strains in asymptomatic neonates as well as detection of G8P[1] strains in diarrheic children support our hypothesis for bidirectional transmission of rotaviruses between humans and cattle and origin of novel strains catalyzed by the age-old traditions and socio-economic conditions in India.

Effect of lithium ion irradiation on the transport and optical properties of Bridgman grown n-type InSb single crystals

Single crystal (100) wafers of n-InSb were implanted with 50 MeV Li3+ ions at various fluences ranging from 10(10) to 10(14) ions/cm(2) at room temperature. Investigations of the optical, electrical, and structural properties of the as-grown, irradiated, annealed wafers were carried out by infrared and Raman spectroscopies, Hall measurements, and high resolution x-ray diffraction (HRXRD). In the case of samples irradiated with an ion fluence of 1.6x10(14) ions/cm(2), electrical measurements at 80 K reveal that there is a decrease in carrier concentration from 8.5x10(15) (for unirradiated) to 1.1x10(15)/cm(3) and an increase in mobility from 5.4x10(4) to 1.67x10(5) cm(2)/V s. The change in carrier concentration is attributed to the creation of electron trap centers induced by ion beam irradiation and the increase in mobility to the formation of electrical inactive complexes. Nevertheless, even with the irradiation at 1.6x10(14) ions/cm(2) fluence the crystalline quality remains largely unaffected, as is seen from HRXRD and Raman studies. (C) 2001 American Institute of Physics.

Toward a Mean Field Formulation of the Babcock-Leighton Type Solar Dynamo. I. α-Coefficient versus Durney's Double-Ring Approach

We develop a model of the solar dynamo in which, on the one hand, we follow the Babcock-Leighton approach to include surface processes, such as the production of poloidal field from the decay of active regions, and, on the other hand, we attempt to develop a mean field theory that can be studied in quantitative detail. One of the main challenges in developing such models is to treat the buoyant rise of the toroidal field and the production of poloidal field from it near the surface. A previous paper by Choudhuri, Schüssler, & Dikpati in 1995 did not incorporate buoyancy. We extend this model by two contrasting methods. In one method, we incorporate the generation of the poloidal field near the solar surface by Durney's procedure of double-ring eruption. In the second method, the poloidal field generation is treated by a positive α-effect concentrated near the solar surface coupled with an algorithm for handling buoyancy. The two methods are found to give qualitatively similar results.

Variable temperature x-ray crystal structure analysis of a type I langbeinite: Rb2Cd2(SO4)(3)

The structure of a type I langbeinite, Rb2Cd2(SO4)(3), displays three different phases, cubic with a = 10.378(5) Angstrom (space group P2(1)3) at room temperature, monoclinic at 120 K with a = 10.328(3), b = 10.322(3), c = 10.325(3) Angstrom, beta = 89.975(1)degrees (space group P2(1)), and orthorhombic at 85 K with a = 10.319(2), b = 10.321(2), c = 10.320(2) Angstrom (space group P2(1)2(1)2(1)), respectively. Precise single-crystal analyses of these phases indicate that Rb2Cd2(SO4)(3) distorts initially from cubic to monoclinic upon cooling followed by a significant reorientation of the SO4 tetrahedra, resulting in an orthorhombic symmetry upon further cooling. The three structures have been established unequivocally using the same crystal. There is no indication of the formation of an intermediate triclinic phase or any lattice disorder as conjectured in several earlier reports on compounds belonging to the type I langbeinite. The bond valence sum analyses of the coordination around the Rb sites indicate asymmetry in the bond strengths which could be the driving force of the ferroelectric behavior in these materials.

A new type II restriction endonuclease, OfoI from nonheterocystous cyanobacterium Oscillatoria foreaui

Although restriction enzymes are widely distributed in nature, many bacterial genera are yet to be explored for the presence of this important class of enzymes. We have purified and characterized a new type II restriction endonuclease, OfoI from a nonheterocyst cyanobacterium Oscillatoria foreaui. The recognition sequence has been determined by primer extension analysis. The purified enzyme OfoI recognizes and cleaves the palindromic hexanucleotide 5'-Cdown arrowYCGRG-3', generating 5'-protruding ends.

Efficient syntheses of benzothiazepines as antagonists for the mitochondrial sodium-calcium exchanger: Potential therapeutics for type II diabetes

Type II diabetes mellitus is a chronic metabolic disorder that can lead to serious cardiovascular, renal, neurologic, and retinal complications. While several drugs are currently prescribed to treat type II diabetes, their efficacy is limited by mechanism-related side effects (weight gain, hypoglycemia, gastrointestinal distress), inadequate efficacy for use as monotherapy, and the development of tolerance to the agents. Consequently, combination therapies are frequently employed to effectively regulate blood glucose levels. We have focused on the mitochondrial sodium-calcium exchanger (mNCE) as a novel target for diabetes drug discovery. We have proposed that inhibition of the mNCE can be used to regulate calcium flux across the mitochondrial membrane, thereby enhancing mitochondrial oxidative metabolism, which in turn enhances glucose-stimulated insulin secretion (GSIS) in the pancreatic beta-cell. In this paper, we report the facile synthesis of benzothiazepines and derivatives by S-alkylation using 2-aminobenzhydrols. The syntheses of other bicyclic analogues based on benzothiazepine, benzothiazecine, benzodiazecine, and benzodiazepine templates are also described. These compounds have been evaluated for their inhibition of mNCE activity, and the results from the structure-activity relationship (SAR) studies are discussed.

Electrical properties of ferroelectric YMnO3 films deposited on n-type Si(111) substrates

YMnO3 thin films were grown on an n-type Si substrate by nebulized spray pyrolysis in the metal-ferroelectric-semiconductor (MFS) configuration. The capacitance-voltage characteristics of the film in the MFS structure exhibit hysteretic behaviour consistent with the polarization charge switching direction, with the memory window decreasing with increase in temperature. The density of the interface states decreases with increasing annealing temperature. Mapping of the silicon energy band gap with the interface states has been carried out. The leakage current, measured in the accumulation region, is lower in well-crystallized thin films and obeys a space-charge limited conduction mechanism. The calculated activation energy from the dc leakage current characteristics of the Arrhenius plot reveals that the activation energy corresponds to oxygen vacancy motion.

Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

The role of defects in carrier type reversal in bismuth doped Ge-Se glasses by photoluminescence spectroscopy

The role played by defects in bringing out n-type conduction in Ge20Se80-xBix and Ge20Se70-xBixTe10 glasses is using investigated photoluminescence (PL) spectroscopy. It was found that for both the systems, the compositions at lower Bi content exhibit luminescence with fine features associated while the compositions that show n-type conduction do not exhibit luminescence. The identification of the associated fine features, carried out by deconvoluting the experimental spectra, reveals that Bi addition brings out a relative diminishing in D+ defects as compared to D- ones. The study gives an overall indication for the role played by native defects in bringing out n-type conduction in Bi-doped glasses.

Synthesis of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) with KSbO(3)-type structure and their magnetic and photocatalytic properties

Synthesis and structure of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) are reported in conjunction with their magnetic and photocatalytic properties. XRD refinements reflect that Bi(3)CrSb(2)O(11), Bi(2)LaCrSb(2)O(11), Bi(2)LaMnSb(2)O(11) and Bi(2)LaFeSb(2)O(11) adopt KSbO(3)-type structure (space group, Pn (3) over bar). The structure can be described through three interpenetrating networks where the first is the (M/Sb)O(6) octahedral network and other two are the identical networks having Bi(6)O(4) composition. The magnetic measurements on Bi(2)LaCrSb(2)O(11) and Bi(2)LaMnSb(2)O(11) show paramagnetic behaviour with magnetic moments close to the expected spin only magnetic moments of Cr(+3) and Mn(+3). The UV-Visible diffuse reflectance spectra are broad and indicate that these materials possess a bandgap of similar to 2 eV. The photocatalytic activity of these materials has been investigated by degrading Malachite Green (MG) under exposure to UV light.