Enantiodivergent total synthesis of microcarpalide from L-tartaric acid

Stereoselective approach for the synthesis of both enantiomers of bio-active decanolactone microcarpalide is described from L-tartaric acid. The synthesis of the key intermediates en route to the natural product is achieved from L-tartaric acid involving the elaboration of gamma-hydroxy amide derived from tartaric acid and ring opening of an epoxide derived from tartaric acid. (C) 2011 Elsevier Ltd. All rights reserved.

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.

Photon-photon total cross-section

We study the total inelastic gamma gamma cross-section and discuss predictions from different models, with a special attention to their dependence on the input parameters. In particular we examine the results from a simple extension of the Regge Pomeron exchange model and those from the eikonalized mini-jet model. We then compare both of them with recent LEP data.

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).

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.

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.

Total peroxidase activity and peroxidase isoforms as modified by salt stress in two cultivars of fox-tail millet with differential salt tolerance

The effect of NaCl on total peroxidase activity, induction of isoperoxidases and lipid peroxidation in 5-day-old seedlings of two contrasting genotypes of Setaria italica L. (Prasad, a salt tolerant cultivar and Lepakshi, a salt susceptible cultivar), was studied. Total peroxidase activity increased under NaCl salinity and the degree of elevation in the activity was salt concentration dependent. Nevertheless, a greater activity was recorded in the tolerant cultivar (cv Prasad) compared to the susceptible (cv Lepakshi) one in all days of sampling. Further, the pattern of isoperoxidases was modified during stress conditions as evident from the electrophoregrams. Although, five acidic isoforms were detected in both cultivars, differences were found between the cultivars. Furthermore, it was observed that acidic isoperoxidases were strongly expressed and an acidic isoperoxidase, A(3p) (27 kDa) is specifically found in the tolerant cultivar (cv Prasad) under NaCl stress. This isoform was partially purified and found to be thermostable with pr 5.5 and the optimum pH 7.4. A close correlation exists between the rate of lipid peroxidation in terms of malonaldehyde (MDA) content and total peroxidase activity per gram fresh weight with salt tolerance of the two cultivars. The tolerant cultivar (cv Prasad) had low MDA content and high total peroxidase activity than the susceptible variety (cv Lepakshi) during salinity stress. (C) 1999 Published by Elsevier Science Ireland Ltd. All rights reserved.

A token-based distributed algorithm for total order atomic broadcast

In this paper, we propose a new token-based distributed algorithm for total order atomic broadcast. We have shown that the proposed algorithm requires lesser number of messages compared to the algorithm where broadcast servers use unicasting to send messages to other broadcast servers. The traditional method of broadcasting requires 3(N - 1) messages to broadcast an application message, where N is the number of broadcast servers present in the system. In this algorithm, the maximum number of token messages required to broadcast an application message is 2N. For a heavily loaded system, the average number of token messages required to broadcast an application message reduces to 2, which is a substantial improvement over the traditional broadcasting approach.

Evaluation and improvement of total transfer capability - A case study

With deregulation, the total transfer capability (TTC) calculation, which is the basis for evaluating available transfer capability (ATC), has become very significant. TTC is an important index in power markets with large volume of inter-area power exchanges and wheeling transactions taking place on an hourly basis. Its computation helps to achieve a viable technical and commercial transmission operation. The aim of the paper is to evaluate TTC in the interconnections and also to improve it using reactive optimization technique and UPFC devices. Computations are carried out for normal and contingency cases such as single line, tie line and generator outages. Base and optimized results are presented, and the results show how reactive optimization and unified power flow controller help to improve the system conditions. In this paper repeated power flow method is used to calculate TTC due to its ease of implementation. A case study is carried out on a 205 bus equivalent system, a part of Indian Southern grid. Parameters like voltage magnitude, L-index, minimum singular value and MW losses are computed to analyze the system performance.

High contrast imaging and thickness determination of graphene with in-column secondary electron microscopy

We report a new method for quantitative estimation of graphene layer thicknesses using high contrast imaging of graphene films on insulating substrates with a scanning electron microscope. By detecting the attenuation of secondary electrons emitted from the substrate with an in-column low-energy electron detector, we have achieved very high thickness-dependent contrast that allows quantitative estimation of thickness up to several graphene layers. The nanometer scale spatial resolution of the electron micrographs also allows a simple structural characterization scheme for graphene, which has been applied to identify faults, wrinkles, voids, and patches of multilayer growth in large-area chemical vapor deposited graphene. We have discussed the factors, such as differential surface charging and electron beam induced current, that affect the contrast of graphene images in detail. (C) 2011 American Institute of Physics. doi:10.1063/1.3608062]

Role of clay content and moisture on characteristics of cement stabilised rammed earth

Rammed earth is an energy efficient and low carbon emission alternative for load bearing walls. This paper attempts to examine the influence of clay content and moisture content on the compressive strength of cement stabilised rammed earth (CSRE) through experimental investigations. Compressive strength of CSRE prisms was monitored both in dry and wet (saturated) conditions. Major conclusions of the study are:(a) Optimum clay content for maximum compressive strength is about 16%, (b) the strength of CSRE is sensitive to the moisture content at the time of testing, (c) Strength in saturated condition is less than half of the dry strength and (d) Water absorption (saturated water content) increases as the clay content of the soil mix increases and it is in the range of 12 to 16% for the CRSE prisms with 8% cement.

A convenient enantiospecific methodology for (-)-(1R,5S)-1,5-dimethylbicyclo[3.3.0]octa-2,7-dione: A formal total synthesis of (-)-ceratopicanol

An enantiospecific formal total synthesis of (-)-ceratopicanol starting from the readily and abundantly available monoterpene (R)-limonene is described. A combination of Claisen rearrangement-intramolecular diazo-ketone cyclopropanation-regiospecific reductive cyclopropane cleavage reactions are employed for the stereo- and regiospecific generation of the two vicinal ring junction quaternary carbon atoms.

Enantiospecific first total synthesis and assignment of absolute configuration of the sesquiterpene (-)-cucumin H

The first total synthesis of the sesquiterpene (-)-cucumin H, a linear triquinane isolated from Macrocystidia cucumis, has been accomplished starting from (R)-limonene employing two different cyclopentannulation methodologies, which in addition to confirming the structure also established the absolute configuration of the natural product.