Synthesis based on cyclohexadienes. Part 25. Total synthesis of (+/-)-allo-cedrol (khusiol)

The first stereoselective total synthesis of (+/-)-allo-cedrol 20, an enantiomer of khusiol and a complex sesquiterpene having a novel tricyclo[5.2.2.0(1,5)]undecane framework, is reported from 8-methoxytricyclo[6.2.2.0(1,6)]dodec-6-en-9-one 6c. The methodology involves preparation of 9-methoxytricyclo[7.2.1.0(1,6)]dodec-6-en-8-one 12 from 6c and its conversion through the compounds 8-benzyloxy-7,7-dimethyl-9-methoxytricyclo[7.2.1.0(1,6)]dodec-5-ene 38, 7-benzyloxy-8-methoxy-2,6,6-trimethyltricyclo[6.2.1.0(1,5)]undecane 48 into 8-methoxy-2,6,6-trimethyltricyclo[6.2.1.0(1,5)]undecan-7-one 49. Wittig reaction of 49 affords the olefin 50 which has been smoothly rearranged into khusione 51. Metal-ammonia reduction of khusione under specific conditions affords (+/-)-allo-cedrol. Thus, bridgehead substitution of a methoxy group by a methyl group is the key reaction in this synthesis. In an alternative strategy, attempted conversion of 8-methoxy-2-methyltricyclo[6.2.1.0(1,5)]undec-5-en-7-one 16 into khusione 37 results in an inseparable mixture of the isomers. A notable observation in this synthesis is the unusual formation of a gamma-alkylated product 27 during Woodward methylation of 16.

Optical and Physical Properties of Atmospheric Aerosols over the Bay of Bengal during ICARB

Simultaneous and collocated measurements of total and hemispherical backscattering coefficients (σ and β, respectively) at three wavelengths, mass size distributions, and columnar spectral aerosol optical depth (AOD) were made onboard an extensive cruise experiment covering, for the first time, the entire Bay of Bengal (BoB) and northern Indian Ocean. The results are synthesized to understand the optical properties of aerosols in the marine atmospheric boundary layer and their dependence on the size distribution. The observations revealed distinct spatial and spectral variations of all the aerosol parameters over the BoB and the presence of strong latitudinal gradients. The size distributions varied spatially, with the majority of accumulation modes decreasing from north to south. The scattering coefficient decreased from very high values (resembling those reported for continental/urban locations) in the northern BoB to very low values seen over near-pristine environments in the southeastern BoB. The average mass scattering efficiency of BoB aerosols was found to be 2.66 ± 0.1 m2 g−1 at 550 nm. The spectral dependence of columnar AOD deviated significantly from that of the scattering coefficients in the northern BoB, implying vertical heterogeneity in the aerosol type in that region. However, a more homogeneous scenario was observed in the southern BoB. Simultaneous lidar and in situ measurements onboard an aircraft over the ocean revealed the presence of elevated aerosol layers of enhanced extinction at altitudes of 1 to 3 km with an offshore extent of a few hundred kilometers. Back-trajectory analyses showed these layers to be associated with advection from west Asia and western India. The large spatial variations and vertical heterogeneity in aerosol properties, revealed by the present study, need to be included in the regional radiative forcing over the Bay of Bengal.

Spatial and vertical heterogeneities in aerosol properties over oceanic regions around India: Implications for radiative forcing

The influence of atmospheric aerosols on Earth's radiation budget and hence climate, though well recognized and extensively investigated in recent years, remains largely uncertain mainly because of the large spatio-temporal heterogeneity and the lack of data with adequate resolution. To characterize this diversity, a major multi-platform field campaign ICARB (Integrated Campaign for Aerosols, gases and Radiation Budget) was carried out during the pre-monsoon period of 2006 over the Indian landmass and surrounding oceans, which was the biggest such campaign ever conducted over this region. Based on the extensive and concurrent measurements of the optical and physical properties of atmospheric aerosols during ICARB, the spatial distribution of aerosol radiative forcing was estimated over the entire Bay of Bengal (BoB), northern Indian Ocean and Arabian Sea (AS) as well as large spatial variations within these regions. Besides being considerably lower than the mean values reported earlier for this region, our studies have revealed large differences in the forcing components between the BoB and the AS. While the regionally averaged aerosol-induced atmospheric forcing efficiency was 31 +/- 6 W m(-2) tau(-1) for the BoB, it was only similar to 18 +/- 7 W m(-2) tau(-1) for the AS. Airborne measurements revealed the presence of strong, elevated aerosol layers even over the oceans, leading to vertical structures in the atmospheric forcing, resulting in significant warming in the lower troposphere. These observations suggest serious climate implications and raise issues ranging from the impact of aerosols on vertical thermal structure of the atmospheric and hence cloud formation processes to monsoon circulation.

Asymmetric total synthesis of erythromycin. 2. Synthesis of an erythronolide A lactone system

In reporting a total synthesis of erythromycin (la) we described in the preceding paper1 the synthesis of the erythronolide A seco acid derivative 2 in optically active form. In this paper we wish to report a successful transformation of 2 to 12 (synthetically equivalent to erythronolide A) via lactonization and also demonstrate that the proper functionalization of a substrate is critical for the successful lactonization.

Asymmetric total synthesis of erythromycin. 3. Total synthesis of erythromycin

In the preceding paper' we described the preparation of the key lactone intermediate la in optically active form. In this paper we report the synthesis of erythromycin (2) from la. In essence,this transformation involves the glycosidation of a suitable derivative of la with L-cladinose and D-desosamine and the generation of the C-9 ketone functionality.

Cyclic AMP in Mycobacteria: Characterization and Functional Role of the Rv1647 Ortholog in Mycobacterium smegmatis{triangledown}

Mycobacterial genomes are endowed with many eukaryote-like nucleotide cyclase genes encoding proteins that can synthesize 3',5'-cyclic AMP (cAMP). However, the roles of cAMP and the need for such redundancy in terms of adenylyl cyclase genes remain unknown. We measured cAMP levels in Mycobacterium smegmatis during growth and under various stress conditions and report the first biochemical and functional characterization of the MSMEG_3780 adenylyl cyclase, whose orthologs in Mycobacterium tuberculosis (Rv1647) and Mycobacterium leprae (ML1399) have been recently characterized in vitro. MSMEG_3780 was important for producing cAMP levels in the logarithmic phase of growth, since the {Delta}MSMEG_3780 strain showed lower intracellular cAMP levels at this stage of growth. cAMP levels decreased in wild-type M. smegmatis under conditions of acid stress but not in the {Delta}MSMEG_3780 strain. This was correlated with a reduction in MSMEG_3780 promoter activity, indicating that the effect of the reduction in cAMP levels on acid stress was caused by a decrease in the transcription of MSMEG_3780. Complementation of the {Delta}MSMEG_3780 strain with the genomic integration of MSMEG_3780 or the Rv1647 gene could restore cAMP levels during logarithmic growth. The Rv1647 promoter was also acid sensitive, emphasizing the biochemical and functional similarities in these two adenylyl cyclases. This study therefore represents the first detailed biochemical and functional analysis of an adenylyl cyclase that is important for maintaining cAMP levels in mycobacteria and underscores the subtle roles that these genes may play in the physiology of the organism.

Surface freshwater from Bay of Bengal runoff and Indonesian Throughflow in the Tropical Indian Ocean

According to recent estimates, the annual total continental runoff into the Bay of Bengal (BoB) is about 2950 km 3, which is more than half that into the entire tropical Indian Ocean (IO). Here we use climatological observations to trace the seasonal pathways of near surface freshwater from BoB runoff and Indonesian Throughflow (ITF) by removing the net contribution from precipitation minus evaporation. North of 20 degrees S, the amount of freshwater from BoB runoff and ITF changes with season in a manner consistent with surface currents from drifters. BoB runoff reaches remote regions of the Arabian Sea; it also crosses the equator in the east to join the ITF. This freshwater subsequently flows west across the southern tropical IO in the South Equatorial Current.

Surprising observation of large anthropogenic aerosol fraction over the ``near-pristine'' southern Bay of Bengal: Climate implications

The Bay of Bengal (BoB), a small oceanic region surrounded by landmasses with distinct natural and anthropogenic activities and under the influence of seasonally changing airmass types, is characterized by a rather complex and highly heterogeneous aerosol environment. Concurrent measurements of the physical, optical, and chemical (offline analysis) properties of BoB aerosols, made onboard extensive ship-cruises and aircraft sorties during Integrated Campaign for Aerosols, gases and Radiation Budget of March-April 2006, and satellite-retrieved aerosol optical depths and derived parameters, were synthesized following a synergistic approach to delineate the anthropogenic fraction to the composite aerosol parameters and its spatial variation. Quite interestingly and contrary to the general belief, our studies revealed that, despite of the very high aerosol loading (in the marine atmospheric boundary layer as well as in the vertical column) over the northern BoB and a steep decreasing gradient toward the southern latitudes, the anthropogenic fraction showed a steady increase from North to South (where no obvious anthropogenic source regions exist). Consequently, the direct radiative forcing at the top of the atmosphere due to anthropogenic aerosols remained nearly constant over the entire BoB with values in the range from -3.3 to -3.6 Wm(-2). This interesting finding, beyond doubts calls for a better understanding of the complex aerosol system over the BoB through more focused field campaigns.

Airborne measurements of aerosol scattering properties above the MABL over Bay of Bengal during W_ICARB - characteristics and spatial gradients

Realizing the importance of aerosol characterization and addressing its spatio-temporal heterogeneities over Bay of Bengal (BoB), campaign mode observations of aerosol parameters were carried out using simultaneous cruise, aircraft and land-based measurements during the Winter Integrated Campaign for Aerosols gases and Radiation Budget (W_ICARB). Under this, airborne measurements of total and hemispheric backscatter coefficients were made over several regions of coastal India and eastern BoB using a three wavelength integrating nephelometer. The measurements include high resolution multi-level (ML) sorties for altitude profiles and bi-level (BL) sorties for spatial gradients within and above the Marine Atmospheric Boundary Layer (MABL) over BoB. The vertical profiles of the scattering coefficients are investigated in light of the information on the vertical structure of the atmospheric stability, which was derived from the collocated GPS (Global Positioning System) aided radiosonde ascents. In general, the altitude profiles revealed that the scattering coefficient remained steady in the convectively well-mixed regions and dropped off above the MABL. This decrease was quite rapid off the Indian mainland, while it was more gradual in the eastern BoB. Investigation on horizontal gradients revealed that the scattering coefficients over northern BoB are 3 to 4 times higher compared to that of central BoB within and above the MABL. A north-south gradient in scattering coefficients is observed over Port Blair in the eastern BoB, with values decreasing from south to north, which is attributed to the similar gradient in the surface wind speed, which can be replicated in the sea salt abundance. The gradients are parameterized using best-fit analytical functions.

Numerical Modelling of the Observed Diurnal Cycle of Indian Monsoon Rainfall

We have analysed the diurnal cycle of rainfall over the Indian region (10S-35N, 60E-100E) using both satellite and in-situ data, and found many interesting features associated with this fundamental, yet under-explored, mode of variability. Since there is a distinct and strong diurnal mode of variability associated with the Indian summer monsoon rainfall, we evaluate the ability of the Weather Research and Forecasting Model (WRF) to simulate the observed diurnal rainfall characteristics. The model (at 54km grid-spacing) is integrated for the month of July, 2006, since this period was particularly favourable for the study of diurnal cycle. We first evaluate the sensitivity of the model to the prescribed sea surface temperature (SST), by using two different SST datasets, namely, Final Analyses (FNL) and Real-time Global (RTG). It was found that with RTG SST the rainfall simulation over central India (CI) was significantly better than that with FNL. On the other hand, over the Bay of Bengal (BoB), rainfall simulated with FNL was marginally better than with RTG. However, the overall performance of RTG SST was found to be better than FNL, and hence it was used for further model simulations. Next, we investigated the role of the convective parameterization scheme on the simulation of diurnal cycle of rainfall. We found that the Kain-Fritsch (KF) scheme performs significantly better than Betts-Miller-Janjić (BMJ) and Grell-Devenyi schemes. We also studied the impact of other physical parameterizations, namely, microphysics, boundary layer, land surface, and the radiation parameterization, on the simulation of diurnal cycle of rainfall, and identified the “best” model configuration. We used this configuration of the “best” model to perform a sensitivity study on the role of various convective components used in the KF scheme. In particular, we studied the role of convective downdrafts, convective timescale, and feedback fraction, on the simulated diurnal cycle of rainfall. The “best” model simulations, in general, show a good agreement with observations. Specifically, (i) Over CI, the simulated diurnal rainfall peak is at 1430 IST, in comparison to the observed 1430-1730 IST peak; (ii) Over Western Ghats and Burmese mountains, the model simulates a diurnal rainfall peak at 1430 IST, as opposed to the observed peak of 1430-1730 IST; (iii) Over Sumatra, both model and observations show a diurnal peak at 1730 IST; (iv) The observed southward propagating diurnal rainfall bands over BoB are weakly simulated by WRF. Besides the diurnal cycle of rainfall, the mean spatial pattern of total rainfall and its partitioning between the convective and stratiform components, are also well simulated. The “best” model configuration was used to conduct two nested simulations with one-way, three-level nesting (54-18-6km) over CI and BoB. While, the 54km and 18km simulations were conducted for the whole of July, 2006, the 6km simulation was carried out for the period 18 - 24 July, 2006. The results of our coarse- and fine-scale numerical simulations of the diurnal cycle of monsoon rainfall will be discussed.

Tracing the source of bottled water using stable isotope techniques

The Indian Summer Monsoon (ISM) precipitation recharges ground water aquifers in a large portion of the Indian subcontinent. Monsoonal precipitation over the Indian region brings moisture from the Arabian Sea and the Bay of Bengal (BoB). A large difference in the salinity of these two reservoirs, owing to the large amount of freshwater discharge from the continental rivers in the case of the BoB and dominating evaporation processes over the Arabian Sea region, allows us to distinguish the isotopic signatures in water originating in these two water bodies. Most bottled water manufacturers exploit the natural resources of groundwater, replenished by the monsoonal precipitation, for bottling purposes. The work presented here relates the isotopic ratios of bottled water to latitude, moisture source and seasonality in precipitation isotope ratios. We investigated the impact of the above factors on the isotopic composition of bottled water. The result shows a strong relationship between isotope ratios in precipitation (obtained from the GNIP data base)/bottled water with latitude. The approach can be used to predict the latitude at which the bottled water was manufactured. The paper provides two alternative approaches to address the site prediction. The limitations of this approach in identifying source locations and the uncertainty in latitude estimations are discussed. Furthermore, the method provided here can also be used as an important forensic tool for exploring the source location of bottled water from other regions. Copyright (C) 2011 John Wiley & Sons, Ltd.

Mechanisms of summer intraseasonal sea surface temperature oscillations in the Bay of Bengal

Intraseasonal variations (ISV) of sea surface temperature (SST) in the Bay of Bengal (BoB) is highest in its northwestern part. An Indian Ocean model forced by QuikSCAT winds and climatological river discharge (QR run) reproduces ISV of SST, albeit with weaker magnitude. Air-sea fluxes, in the presence of a shallow mixed layer, efficiently effect intraseasonal SST fluctuations. Warming during intraseasonal events is smaller (<1°C) for June - July period and larger (1.5° to 2°C) during September, the latter due to a thinner mixed layer. To examine the effect of salinity on ISV, the model was run by artificially increasing the salinity (NORR run) and by decreasing it (MAHA10 run). In NORR, both rainfall and river discharge were switched off and in MAHA10 the discharge by river Mahanadi was increased tenfold. The spatial pattern of ISV as well as its periodicity was similar in QR, NORR and MAHA10. The ISV was stronger in NORR and weaker in MAHA10, compared to QR. In NORR, both intraseasonal warming and cooling were higher than in QR, the former due to reduced air-sea heat loss as the mean SST was lower, and the latter due to enhanced subsurface processes resulting from weaker stratification. In MAHA10, both warming and cooling were lower than in QR, the former due to higher air-sea heat loss owing to higher mean SST, and the latter due to weak subsurface processes resulting from stronger stratification. These model experiments suggest that salinity effects are crucial in determining amplitudes of intraseasonal SST variations in the BoB.

Si isotope variability in Proterozoic cherts

We report Si-isotopic compositions of 75 sedimentologically and petrographically characterized chert samples with ages ranging from similar to 2600 to 750 Ma using multi-collector inductively coupled plasma mass spectrometry. delta Si-30 values of the cherts analyzed in this study show a similar to 7 parts per thousand range, from -4.29 to +2.85. This variability can be explained in part by (1) simple mixing of silica derived from continental (higher delta Si-30) and hydrothermal (lower delta Si-30) sources, (2) multiple mechanisms of silica precipitation and (3) Rayleigh-type fractionations within pore waters of individual basins. We observe similar to 3 parts per thousand variation in peritidal cherts from a single Neoproterozoic sedimentary basin (Spitsbergen). This variation can be explained by Rayleigh-type fractionation during precipitation from silica-saturated porewaters. In some samples, post-dissolution and reprecipitation of silica could have added to this effect. Our data also indicate that peritidal cherts are enriched in the heavier isotopes of Si whereas basinal cherts associated with banded iron formations (BIF) show lower delta Si-30. This difference could partly be due to Si being derived from hydrothermal sources in BIFs. We postulate that the difference in delta Si-30 between non-BIF and BIF cherts is consistent with the contrasting genesis of these deposits. Low delta Si-30 in BIF is consistent with laboratory experiments showing that silica adsorbed onto Fe-hydroxide particles preferentially incorporates lighter Si isotopes. Despite large intrabasinal variation and environmental differences, the data show a clear pattern of secular variation. Low delta Si-30 in Archean cherts is consistent with a dominantly hydrothermal source of silica to the oceans at that time. The monotonically increasing delta Si-30 from 3.8 to 1.5 Ga appears to reflect a general increase in continental versus hydrothermal sources of Si in seawater, as well as the preferential removal of lighter Si isotopes during silica precipitation in iron-associated cherts from silica-saturated seawater. The highest delta Si-30 values are observed in 1.5 Ga peritidal cherts; in part, these enriched values could reflect increasing sequestration of light silica during soil-forming processes, thus, delivering relatively heavy dissolved silica to the oceans from continental sources. The causes behind the reversal in trend towards lower delta Si-30 in cherts younger than 1.5 Ga old are less clear. Cherts deposited 1800-1900 Ma are especially low delta Si-30, a possible indication of transiently strong hydrothermal input at this time. (C) 2012 Elsevier Ltd. All rights reserved.

A trust model for routing in MANETs: a cognitive agents based approach

Mobile ad hoc networks (MANETs) is one of the successful wireless network paradigms which offers unrestricted mobility without depending on any underlying infrastructure. MANETs have become an exciting and im- portant technology in recent years because of the rapid proliferation of variety of wireless devices, and increased use of ad hoc networks in various applications. Like any other networks, MANETs are also prone to variety of attacks majorly in routing side, most of the proposed secured routing solutions based on cryptography and authentication methods have greater overhead, which results in latency problems and resource crunch problems, especially in energy side. The successful working of these mechanisms also depends on secured key management involving a trusted third authority, which is generally difficult to implement in MANET environ-ment due to volatile topology. Designing a secured routing algorithm for MANETs which incorporates the notion of trust without maintaining any trusted third entity is an interesting research problem in recent years. This paper propose a new trust model based on cognitive reasoning,which associates the notion of trust with all the member nodes of MANETs using a novel Behaviors-Observations- Beliefs(BOB) model. These trust values are used for detec- tion and prevention of malicious and dishonest nodes while routing the data. The proposed trust model works with the DTM-DSR protocol, which involves computation of direct trust between any two nodes using cognitive knowledge. We have taken care of trust fading over time, rewards, and penalties while computing the trustworthiness of a node and also route. A simulator is developed for testing the proposed algorithm, the results of experiments shows incorporation of cognitive reasoning for computation of trust in routing effectively detects intrusions in MANET environment, and generates more reliable routes for secured routing of data.