Synthetic studies toward geranylated PPAP natural products oblongifolin A, oblongifolin D, and enervosanone

A concise approach of general utility toward mono- and di-geranylated PPAP frameworks employing `reconstructive aldol cyclization' as the key step is delineated. (C) 2012 Elsevier Ltd. All rights reserved.

Enantioselective syntheses of bioactive epoxyquinone natural products (+)-harveynone and (-)-asperpentyn

Stereo- and enantioselective syntheses of (+)-harveynone and (-)-asperpentyn are reported. (C) 2012 Elsevier Ltd. All rights reserved.

Model synthetic studies toward jiadifenin and majucin type seco-prezizaane natural products via a stereo- and enantioselective approach

A concise stereo- and enantioselective approach to seco-prezizaane sesquiterpenoids, leading to the acquisition of two bicyclic fragments, is delineated. (c) 2012 Elsevier Ltd. All rights reserved.

Study of conjugate natural convection between vertical coaxial rectangular cylinders

Laminar natural convection between two coaxial vertical rectangular cylinders is numerically studied in this work. The outer cylinder is connected with vertical rectangular inlet and outlet pipes. The inner cylinder dissipates volumetric heat. The fluid flow and heat transfer characteristics between the cylinders are analyzed in detail for various Grashof numbers. The heat transfer rates on the individual faces of the inner cylinder are reported. The bottom face of the inner cylinder is found to associate with much higher heat rates than those of the other faces. The average Nusselt number on bottom face is more than 2.5 times of the Nusselt number averaged on all the faces. At a given elevation, local Nusselt number on the inner cylinder faces increases towards cylinder edges. The effect of thermal condition of the walls of outer cylinder, inlet and outlet on the natural convection is analyzed. The thermal condition shows strong qualitative and quantitative impact on the fluid flow and heat transfer. The variation of induced flow rate, dimensionless maximum temperature and average Nusselt numbers with Grashof number is studied. Correlations for dimensionless buoyancy-induced mass flow rate and temperature maximum are presented. (c) 2012 Elsevier Ltd. All rights reserved.

Natural convection in a series of thermally interacting cavities with wall mounted heaters

Laminar natural convection in a series of thermally interacting cavities is numerically studied. Each cavity consists of a conducting bottom wall with a surface mounted heater. The side walls of the cavities are isothermally cooled. Each cavity thermally interacts with its adjacent cavities through the conducting walls. Flow and heat transfer characteristics are studied in detail for various Rayleigh numbers. The convection characteristics in multiple cavities are compared with those in single independent cavity. The thermal interaction between the cavities results in lower temperatures compared with those in independent cavities. While heat is rejected into the adjacent upper cavity through some portion of the conducting wall, heat is received from the adjacent cavity through the remaining portion of the wall. The influence of substrate conductivity on heat exchange between adjacent cavities are examined. Substrate conductivity shows strong effect on temperature distribution. When cooling at both vertical sides is changed to one side cooling, the heat transfer characteristics are changed drastically and many interesting flow features are observed. Effects of cavity aspect ratio is studied and higher heat transfer rates are observed at higher aspect ratios. Correlations for dimensionless temperature maximum and average Nusselt number are presented in terms of Rayleigh number.

Stability of Adult Emergence and Activity/Rest Rhythms in Fruit Flies Drosophila melanogaster under Semi-Natural Condition

Here we report the results of a study aimed at examining stability of adult emergence and activity/rest rhythms under seminatural conditions (henceforth SN), in four large outbred fruit fly Drosophila melanogaster populations, selected for emergence in a narrow window of time under laboratory (henceforth LAB) light/dark (LD) cycles. When assessed under LAB, selected flies display enhanced stability in terms of higher amplitude, synchrony and accuracy in emergence and activity rhythms compared to controls. The present study was conducted to assess whether such differences in stability between selected and control populations, persist under SN where several gradually changing time-cues are present in their strongest form. The study revealed that under SN, emergence waveform of selected flies was modified, with even more enhanced peak and narrower gate-width compared to those observed in the LAB and compared to control populations in SN. Furthermore, flies from selected populations continued to exhibit enhanced synchrony and accuracy in their emergence and activity rhythms under SN compared to controls. Further analysis of zeitgeber effects revealed that enhanced stability in the rhythmicity of selected flies under SN was primarily due to increased sensitivity to light because emergence and activity rhythms of selected flies were as stable as controls under temperature cycles. These results thus suggest that stability of circadian rhythms in fruit flies D. melanogaster, which evolved as a consequence of selection for emergence in a narrow window of time under weak zeitgeber condition of LAB, persists robustly in the face of day-to-day variations in cycling environmental factors of nature.

An approach toward the synthesis of PPAP natural product garsubellin A: construction of the tricyclic core

In a study directed toward the bioactive natural product garsubellin A, an expedient route to the bicyclo 3.3.1]nonan-9-one bearing tricyclic core, with a bridgehead anchored tetrahydrofuran ring, is delineated. The approach emanating from commercially available dimedone involved a DIBAL-H mediated retro aldol/re-aldol cyclization cascade and a PCC mediated oxidative cyclization as the key steps. (C) 2013 Elsevier Ltd. All rights reserved.

Total synthesis and determination of the absolute configuration of 5,6-Dihydro-alpha-pyrone natural product synargentolide B

Enantiospecific total synthesis and determination of the absolute stereochemistry of the alpha-pyrone-containing natural product synargentolide B were accomplished. The absolute stereochemistry of the natural product was established by synthesizing the possible diastereomers and comparison of the data with those reported for the natural product. During the process, total synthesis of the putative structure of related natural product 6R-1S,2R,SR,6S-(tetraacetyloxy)-3E-heptenyl]-5,6-dihydro-2H-pyran-2-o ne was also accomplished and confirmed by X-ray crystal structure analysis. Wittig-Horner reaction of a chiral phosphonate derived from (S)-lactic acid and ring-closing metathesis were the key reactions during the course of the total synthesis.

Natural motion of one-dimensional flexible objects using minimization approaches

For one-dimensional flexible objects such as ropes, chains, hair, the assumption of constant length is realistic for large-scale 3D motion. Moreover, when the motion or disturbance at one end gradually dies down along the curve defining the one-dimensional flexible objects, the motion appears ``natural''. This paper presents a purely geometric and kinematic approach for deriving more natural and length-preserving transformations of planar and spatial curves. Techniques from variational calculus are used to determine analytical conditions and it is shown that the velocity at any point on the curve must be along the tangent at that point for preserving the length and to yield the feature of diminishing motion. It is shown that for the special case of a straight line, the analytical conditions lead to the classical tractrix curve solution. Since analytical solutions exist for a tractrix curve, the motion of a piecewise linear curve can be solved in closed-form and thus can be applied for the resolution of redundancy in hyper-redundant robots. Simulation results for several planar and spatial curves and various input motions of one end are used to illustrate the features of motion damping and eventual alignment with the perturbation vector.

Interleaved winding and suppression of natural frequencies

Ideally, it is desirable to design and manufacture a transformer winding that can render all its internal resonances non-excitable. This study examines the effectiveness of an interleaved winding in achieving this goal. While investigating its effectiveness, it led to the establishment of a much desired theoretical basis that reinforces the reasons put forward in the literature to explain internal insulation failures observed in interleaved windings used in extra high voltage (EHV) transformers. Numerical calculations along with experimental verification on actual transformer windings are presented. This study reveals that most of the natural frequencies that are normally non-excitable in the line and neutral current responses of an interleaved winding have been rendered excitable in the disk-to-disk voltages, thus, providing favourable conditions for insulation overstress because of resonant overvoltages. Prevalence of such a condition is an inherent characteristic of interleaved windings.

Study of buoyant jets in natural ventilation of a model room

Buoyant jets in natural ventilation of a model room with water as the fluid medium have been studied. A constant heat flux has been maintained on the bottom surface of the room. The buoyancy causes flow to enter through the bottom opening and leave through the top opening. The shadowgraph technique is used for visualization. At the inlet, a negatively buoyant jet is observed, whereas a positively buoyant jet is observed at the outlet. The theoretical results for the centerline trajectories of these buoyant jets using both Gaussian and top-hat profiles are discussed considering the variation of the entrainment coefficient with the local Froude number and the variation of the spreading ratio of buoyancy to velocity profile with the distance from the source. The shape of the profiles is found to evolve from top-hat to Gaussian geometry.

Effect of a natural mutation in the 5 ` untranslated region on the translational control of p53 mRNA

Tumor-suppressor protein p53, the `guardian of the genome', is critical in maintaining cellular homeostasis and genomic stability. Earlier, we have reported the discovery of internal ribosome entry sites (IRESs) within the p53 mRNA that regulate the translation of the full length and its N-terminal-truncated isoform, Delta N-p53. Polypyrimidine tract-binding protein (PTB) is an IRES trans-acting factor that positively regulates the IRES activities of both p53 isoforms by relocating from nucleus to the cytoplasm during stress conditions. Here we have demonstrated the putative contact points of PTB on the p53 IRES RNA. Studies on mutations that occur naturally in the 5' untranslated region (5' UTR) in p53 mRNA were lacking. We have investigated a naturally occurring C-to-T single-nucleotide polymorphism (SNP) first reported in human melanoma tumors. This SNP is at position 119 in the 5' UTR of p53 mRNA and we demonstrate that it has consequences on the translational control of p53. Introduction of this SNP has led to decrease in cap-independent translation from p53 5' UTR in bicistronic reporter assay. Further, the effects of this SNP on cap-independent translation have been studied in the context of p53 cDNA as well. Interestingly, the 5' UTR with this SNP has shown reduced binding to PTB that can be corroborated to its weaker IRES activity. Previously, it has been shown that G2-M checkpoint, DNA-damaging stress and oncogenic insult favor IRES-mediated translation. Under similar conditions, we demonstrate that this SNP interferes with the enhancement of the IRES activity of the 5' UTR. Taken together, the results demonstrate for the first time that SNP in the 5' UTR of the p53 mRNA might have a role in translational control of this critical tumor-suppressor gene.

Stable atmospheric methane in the 2000s: key-role of emissions from natural wetlands

Two atmospheric inversions (one fine-resolved and one process-discriminating) and a process-based model for land surface exchanges are brought together to analyse the variations of methane emissions from 1990 to 2009. A focus is put on the role of natural wetlands and on the years 2000-2006, a period of stable atmospheric concentrations. From 1990 to 2000, the top-down and bottom-up visions agree on the time-phasing of global total and wetland emission anomalies. The process-discriminating inversion indicates that wetlands dominate the time-variability of methane emissions (90% of the total variability). The contribution of tropical wetlands to the anomalies is found to be large, especially during the post-Pinatubo years (global negative anomalies with minima between -41 and -19 Tg yr(-1) in 1992) and during the alternate 1997-1998 El-Nino/1998-1999 La-Nina (maximal anomalies in tropical regions between +16 and +22 Tg yr(-1) for the inversions and anomalies due to tropical wetlands between +12 and +17 Tg yr(-1) for the process-based model). Between 2000 and 2006, during the stagnation of methane concentrations in the atmosphere, the top-down and bottom-up approaches agree on the fact that South America is the main region contributing to anomalies in natural wetland emissions, but they disagree on the sign and magnitude of the flux trend in the Amazon basin. A negative trend (-3.9 +/- 1.3 Tg yr(-1)) is inferred by the process-discriminating inversion whereas a positive trend (+1.3 +/- 0.3 Tg yr(-1)) is found by the process model. Although processed-based models have their own caveats and may not take into account all processes, the positive trend found by the B-U approach is considered more likely because it is a robust feature of the process-based model, consistent with analysed precipitations and the satellite-derived extent of inundated areas. On the contrary, the surface-data based inversions lack constraints for South America. This result suggests the need for a re-interpretation of the large increase found in anthropogenic methane inventories after 2000.