Mechanically activated synthesis of nanocrystalline powders of ferroelectric bismuth vanadate

Mechanical milling of a stoichiometric mixture of Bi2O3 and V2O5 yielded nanosized powders of bismuth vanadate, Bi2VO5.5 (BN). Structural evolution of the desired BiV phase, through an intermediate product (BiVO4), was monitored by subjecting the powders, ball milled for various durations to X-ray powder diffraction (XRD), differential thermal analysis (DTA), and transmission electron microscopic (TEM) studies. XRD studies indicate that the relative amount of the BiV phase present in the ball-milled mixture increases with increase in milling time and its formation reaches completion within 54 h of milling. Assynthesized powders were found to stabilize in the high-temperature tetragonal (gamma) phase. DTA analyses of the powders milled for various durations suggest that the BN phase-formation temperature decreases with increase in milling time. The nanometric size (30 nm) of the crystallites in the final product was confirmed by TEM and XRD studies. TEM studies clearly demonstrate the growth of BiV on Bi2O3 crystallites. (C) 1999 Academic Press.

Stereoselective total synthesis of (+/-)-tochuinyl acetate and (+/-)-dihydrotochuinyl acetates

Details of the first total synthesis of the marine natural product dihydrotochuinyl acetate is described. Cyclopentenone annulation of p-methylacetophenone via a Claisen rearrangement-Wacker oxidation based sequence generated the cyclopentenone 3, a known precursor for the sesquiterpenes cuparene, laurene, alpha-cuparenone and beta-cuparenones. Conversion of the ketone moiety into a carboxylate followed by stereoselective alkylation and reduction transformed the cyclopentenone 3 into the primary alcohol 19. Birch reduction of the alcohol 19 followed by acetylation furnished (+/-)-dihydrotochuinyl acetate, whereas direct acetylation of 19 furnished (+/-)-tochuinyl acetate. (C) 1998 Elsevier Science Ltd. All rights reserved.

Rearrangement approaches to sesquiterpenes containing multiple contiguous quaternary carbon atoms. Total synthesis of (+/-)-myltayl-8(12)-ene and (+/-)-6-epijunicedranol

Details of the first total syntheses of the sesquiterpenes myltayl-8(12)-ene and 6-epijunicedran-8-ol are described. The aldehyde 13, obtained by Claisen rearrangement of cyclogeraniol, was transformed into the dienones 12 and 18. Boron trifluoride-diethyl ether mediated cyclization and rearrangement transformed the dienones 12 and 18 into the tricyclic ketones 16 and 17, efficiently creating three and four contiguous quaternary carbon atoms, respectively. Wittig methylenation of 16 furnished (+/-)-myltayl-8(12)-ene (11), whereas reduction of the ketone 17 furnished (+/-)-6-epijunicedranol (23).

Regioselective synthesis of bicyclo[4.2.1]nonane-2,8-diones via BF3.Et2O mediated intramolecular diazo ketone insertion reaction

Treatment of the diazo diones 11a-d with boron trifluoride diethyl etherate furnished the bicyclo[4.2.1]nonane-2,g-diones 15a-d in a highly regioselective manner. (C) 1999 Elsevier Science Ltd. All rights reserved.

Spiroannulation of a cyclopentane ring. Synthesis of spiro[4.n](n+5)alk-2-en-1-ones

A methodology based on Claisen rearrangement-Wacker oxidation and intramolecular aldol condensation strategy starting from cyclic ketones leading to spiro[4.n](n+5)alk-2-en-1-ones has been developed. Thus one-pot Claisen rearrangement of the alkyl alcohols 6a-c furnished the aldehydes 8a-c, which on regiospecific oxidation using Wacker conditions generated the keto-aldehydes 9a-c. Finally, intramolecular aldol condensation transformed the keto-aldehydes 9a-c into spiroannulated products 10a-c.

Synthesis based on cyclohexadienes: Part 26 - Total synthesis of some naturally occurring phthalides from Alternaria species

Total synthesis of the naturally occurring phytotoxic phthalides, silvaticol 7, zinniol 5 and the phthalides 1 and 2, is reported from the substrate 16 derived from the Alder-Rickert reaction of 1-methoxy-2-methyl-3-trimethylslyloxycyclohexa-1,3-diene 15 with dimethyl acetylenedicarboxylate.

Synthesis of ASIPs for DSP algorithms

ASICs offer the best realization of DSP algorithms in terms of performance, but the cost is prohibitive, especially when the volumes involved are low. However, if the architecture synthesis trajectory for such algorithms is such that the target architecture can be identified as an interconnection of elementary parameterized computational structures, then it is possible to attain a close match, both in terms of performance and power with respect to an ASIC, for any algorithmic parameters of the given algorithm. Such an architecture is weakly programmable (configurable) and can be viewed as an application specific integrated processor (ASIP). In this work, we present a methodology to synthesize ASIPs for DSP algorithms. (C) 1999 Elsevier Science B.V. All rights reserved.

Synthesis of inorganic solids using microwaves

Use of microwaves in the synthesis of materials is gaining importance. Microwave-assisted synthesis is generally much faster, cleaner, and more economical than the conventional methods. A variety of materials such as carbides, nitrides, complex oxides, silicides, zeolites, apatite, etc. have been synthesized using microwaves. Many of these are of industrial and technological importance. An understanding of the microwave interaction with materials has been based on concepts of dielectric heating and of the resonance absorption due to rotational excitation. This review presents a summary of recent reports of microwave synthesis of inorganic materials. Various observations regarding microwave interaction with materials are also briefly discussed.

Synthesis of mesoporous materials based on titanium(IV)oxide and titanium nitride

Nanoparticles of titania were obtained by the controlled hydrolysis of Ti(i-OC3H7)(4) in the reverse micelles of dodecylamine derived from dodecylamine-isopropanol-water solution (water/oil microemulsion). The mesolamellar phase based on titanium nitride (TiN) was obtained by first decomposing TiN atleast partially using the 1:1 solution of acid mixture (HF and HNO3 in the ratio of 9:1) in water and then templating onto the cationic surfactant namely, cetyltrimethylammaniumbromide (abbreviated as CTAB) at 80 degrees C. The synthesis of mesolamellar phase based on TiN involves the charge matched templating approach following the counter-ion mediated pathway. The samples thus obtained were characterized by small angle x-ray diffraction using Cuk(a) radiation, scanning electron microscopy and transmission electron microscopy, which indicated some satisfactory results. (C) 1999 Acta Metallurgica Inc.

Synthesis of metastable, wurzite-based zinc oxide-cobalt(II) oxide solid solutions by spray pyrolysis

Aqueous solutions of acetates and nitrates of zinc and cobalt have been spray decomposed to study the production of extended solid solutions in the ZnO-CoO system. Examination of the products of a variety of synthesis conditions indicates that up to 70% CoO may be retained in the solid solution in the wurzite phase, even though a comparison of the equilibrium solubility in the phase diagram might be expected to favor the formation of a rock-salt-based solid solution.

Synthesis of nonlinear controller to recover an unstable aircraft from poststall regime

Dynamics of the aircraft configuration considered in this paper show a unique characteristic in that there are no stable attractors in the entire high angle-of-attack flight envelope. As a result, once the aircraft has departed from the normal flight regime, no standard technique can be applied to recover the aircraft. In this paper, using feedback linearization technique, a nonlinear controller is designed at high angles of attack, which is engaged after the aircraft departs from normal flight regime. This controller stabilizes the aircraft into a stable spin. Then a set of synthetic pilot inputs is applied to cause an automatic transition from the spin equilibrium to low angles of attack where the second controller is connected. This controller is a normal gain-scheduled controller designed to have a large domain of attraction at low angles of attack. It traps the aircraft into a low angle-of-attack level flight. This entire concept of recovery has been verified using six-degrees-of-freedom nonlinear simulation. Feedback linearization technique used to design a controller ensures internal stability only if the nonlinear plant has stable zero dynamics. Because zero dynamics depend on the selection of outputs, a new method of choosing outputs is described to obtain a plant that has stable zero dynamics. Certain important aspects pertaining to the implementation of a feedback linearization-based controller are also discussed.

Synthesis of single-walled carbon nanotubes using binary (Fe, Co, Ni) alloy nanoparticles prepared in situ by the reduction of oxide solid solutions

Passing a H-2-CH4 mixture over oxide spinels containing two transition elements as in Mg0.8MyMz'Al2O4 (M, M' = Fe, Co or Ni, y + z = 0.2) at 1070 degrees C produces small alloy nanoparticles which enable the formation of carbon nanotubes. Surface area measurements are found to be useful for assessing the yield and quality of the nanotubes. Good-quality single-walled nanotubes (SWNTs) have been obtained in high yields with the FeCo alloy nanoparticles, as evidenced by transmission electron microscope images and surface area measurements. The diameter of the SWNTs is in the 0.8-5 nm range, and the multiwalled nanotubes, found occasionally, possess very few graphite layers. (C) 1999 Elsevier Science B.V. All rights reserved.

Synthesis of two designed hairpin peptides on a newly developed 1,6-hexanediol diacrylate (HDODA)-crosslinked polystyrene resin

Synthesis of two designed hairpin peptides on 1,6-hexanediol diacrylate crosslinked polystyrene support using the standard solid phase methodology is described. Both the peptides are obtained in high yield and purity. The new polymeric system is an ideal support for the synthesis of hairpin peptides, which is a very difficult task by the solid phase method.

Enantioselective total synthesis of macrosphelides A and E

Enantioselective synthesis of 16-membered trilactone macrolides, macrosphelide A and E from (S)-lactic acid is described. Key features of the synthesis include the utility of a hitherto unexplored beta-ketophosphonate derived from lactic acid and Yamaguchi lactonization leading to the title compounds. (C) 2011 Elsevier Ltd. All rights reserved.

Total Synthesis of Gabosine H

Stereoselective total synthesis and assignment of the absolute configuration of the keto carba sugar gabosine H is presented. Pivotal reactions in the sequence include desymmetrization of the dimethylamide of tartaric acid and ring-closing metathesis.