Radical cyclization strategies to terpenoids; syntheses of (±)-β-cuparenone, (±)-laurene and epilaurenes

Radical cyclization of the bromide Image , obtained in 5 steps from the ketone Image , furnished exclusively Image Image 6-endo trig cyclization with out any observable amount of 5-exo trig product Image . 5-Exo dig radical cyclizatlon of the bromo acetate Image , prepared from Image Image the aldehyde Image , followed by routine transformations furnished the cyclopentenone Image , an immediate precursor to β-cuparenone (Image ). Similarly, total synthesis of laurenes Image and Image was achieved Image the 5-exo dig radical cyclization of the xanthate Image , obtained from the aldehyde Image .Syntheses to title compounds based on 5-exo-dig radical cyclisation, along with two unsuccessful approaches to cuparene, are described.

A Comparative Study of the Effect of Metallic Au and ReO3 Nanoparticles on the Performance of Silicon Solar Cells

The influence of gold (similar to 35 nm diameter) as well as ReO3 (similar to 17 nm diameter) nanoparticles placed atop silicon photovoltaic devices on absorption and photocurrent generation has been investigated. The nanoparticles improve the power transmission into the semiconductor and consequently, the photocurrent response at wavelengths corresponding to plasmon absorption. An increase in short circuit current up to 4.5% under simulated solar irradiation was observed with the ReO3 nanoparticles, while the gold nanoparticles showed enhancements up to 6.5%. The increase in photocurrent is observed at wavelengths corresponding to the maxima in the surface plasmon resonance absorption spectra. (C) 2010 The Japan Society of Applied Physics

Biomass gasification: Environmentally sound technology for decentralized power generation, a case study from India

This study aims at understanding the need for decentralized power generation systems and to explore the potential, feasibility and environmental implications of biomass gasifier-based electricity generation systems for village electrification. Electricity needs of villages are in the range of 5–20 kW depending on the size of the village. Decentralized power generation systems are desirable for low load village situations as the cost of power transmission lines is reduced and transmission and distribution losses are minimised. A biomass gasifier-based electricity generation system is one of the feasible options; the technology is readily available and has already been field tested. To meet the lighting and stationary power needs of 500,000 villages in India the land required is only 16 Mha compared to over 100 Mha of degraded land available for tree planting. In fact all the 95 Mt of woody biomass required for gasification could be obtained through biomass conservation programmes such as biogas and improved cook stoves. Thus dedication of land for energy plantations may not be required. A shift to a biomass gasifier-based power generation system leads to local benefits such as village self reliance, local employment and skill generation and promotion of in situ plant diversity plus global benefits like no net CO2 emission (as sustainable biomass harvests are possible) and a reduction in CO2 emissions (when used to substitute thermal power and diesel in irrigation pump sets).

Gas-liquid nucleation at large metastability: unusual features and a new formalism

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

Total synthese of (±)-cyclolaurene, (±)-epicylolaurene and (±)-?-cuparenones

The first total synthesis of (±)-cyclolaurene (Image ) and (±)-epicyclolaurene (Image ), and a new route to (±)-?-cuparenone (Image ) are reported. Thus, orthoester Claisen rearrangement of the cinnamyl alcohol Image furnished the eneester Image . Anhydrous CuSO, catalysed intramolecular cyclopropanation of the diazoketone derived from the ene-acid Image , generated a diastereoisomeric mixture of cyclopropyl ketone Image . The Huang-Minlon reduction of the ketones Image and Image furnished the cyclolaurene (Image ) and epicyclolaurene (Image ), whereas regiospecific ring cleavage using lithium in liquid ammonia furnished the ?-cuparenone (Image ).

Community-based Natural Resource Management: Issues and Cases from South Asia

Community-based natural resource management (CBNRM) is the joint management of natural resources by a community based on a community strategy, through a participatory mechanism involving all legitimate stakeholders. The approach is community-based in that the communities managing the resources have the legal rights, the local institutions and the economic incentives to take substantial responsibility for sustained use of these resources. This implies that the community plays an active role in the management of natural resources, not because it asserts sole ownership over them, but because it can claim participation in their management and benefits for practical and technical reasons1–4. This approach emerged as the dominant conservation concept in the late 1970s and early 1980s, of the disillusionment with the developmental state. Governments across South and South East Asia, Africa and Latin America have adopted and implemented CBNRM in various ways, viz. through sectoral programmes such as forestry, irrigation or wildlife management, multisectoral programmes such as watershed development and efforts towards political devolution. In India, the principle of decentralization through ‘gram swaraj’ was introduced by Mahatma Gandhi. The 73rd and 74th constitution amendments in 1992 gave impetus to the decentralized planning at panchayat levels through the creation of a statutory three-level local self-government structure5,6. The strength of this book is that it includes chapters by CBNRM advocates based on six seemingly innovative initiatives being implemented by nongovernmental organizations (NGOs) in ecologically vulnerable regions of South Asia: two in the Himalayas (watershed development programme in Lingmutechhu, Bhuthan and Thalisain tehsil, Paudi Grahwal District, Uttarakhand), three in semi-arid parts of western India (watershed development in Hivre Bazar, Maharashtra and Nathugadh village, Gujarat and water-harvesting structures in Gopalapura, Rajasthan) and one in the flood-plains of the Brahmaputra–Jamuna (Char land, Galibanda and Jamalpur districts, Bangladesh). Watersheds in semi-arid regions fall in the low-rainfall region (500–700 mm) and suffer the vagaries of drought 2–3 years in every five-year cycle. In all these locations, the major occupation is agriculture, most of which is rainfed or dry. The other two cases (in Uttarakhand) fall in the Himalayan region (temperate/sub-temperate climate), which has witnessed extensive deforestation in the last century and is now considered as one of the most vulnerable locations in South Asia. Terraced agriculture is being practised in these locations for a long time. The last case (Gono Chetona) falls in the Brahmaputra–Jamuna charlands which are the most ecologically vulnerable regions in the sub-continent with constantly changing landscape. Agriculture and livestock rearing are the main occupations, and there is substantial seasonal emigration for wage labour by the adult males. River erosion and floods force the people to adopt a semi-migratory lifestyle. The book attempts to analyse the potential as well as limitations of NGOdriven CBNRM endeavours across agroclimatic regions of South Asia with emphasis on four intrinsically linked normative concerns, namely sustainability, livelihood enhancement, equity and demographic decentralization in chapters 2–7. Comparative analysis of these case studies done in chapter 8, highlights the issues that require further research while portraying the strengths and limits of NGO-driven CBNRM. In Hivre Bazar, the post-watershed intervention scenario is such that farmers often grow three crops in a year – kharif bajra, rabi jowar and summer vegetable crops. Productivity has increased in the dry lands due to improvement in soil moisture levels. The revival of johads in Gopalpura has led to the proliferation of wheat and increased productivity. In Lingmuteychhu, productivity gains have also arisen, but more due to the introduction of both local and high-yielding, new varieties as opposed to increased water availability. In the case of Gono Chetona, improvements have come due to diversification of agriculture; for example, the promotion of vegetable gardens. CBNRM interventions in most cases have also led to new avenues of employment and income generation. The synthesis shows that CBNRM efforts have made significant contributions to livelihood enhancement and only limited gains in terms of collective action for sustainable and equitable access to benefits and continuing resource use, and in terms of democratic decentralization, contrary to the objectives of the programme. Livelihood benefits include improvements in availability of livelihood support resources (fuelwood, fodder, drinking water), increased productivity (including diversification of cropping pattern) in agriculture and allied activities, and new sources of livelihood. However, NGO-driven CBNRM has not met its goal of providing ‘alternative’ forms of ‘development’ due to impediments of state policy, short-sighted vision of implementers and confrontation with the socio-ecological reality of the region, which almost always are that of fragmented communities (or communities in flux) with unequal dependence and access to land and other natural resources along with great gender imbalances. Appalling, however, is the general absence of recognition of the importance of and the will to explore practical ways to bring about equitable resource transfer or benefit-sharing and the consequent innovations in this respect that are evident in the pioneering community initiatives such as pani panchayat, etc. Pertaining to the gains on the ecological sustainability front, Hivre Bazar and Thalisain initiatives through active participation of villagers have made significant regeneration of the water table within the village, and mechanisms such as ban on number of bore wells, the regulation of cropping pattern, restrictions on felling of trees and free grazing to ensure that in the future, the groundwater is neither over-exploited nor its recharge capability impaired. Nevertheless, the longterm sustainability of the interventions in the case of Ghoga and Gopalpura initiatives as the focus has been mostly on regeneration of resources, and less on regulating the use of regenerated resources. Further, in Lingmuteychhu and Gono Chetona, the interventions are mainly household-based and the focus has been less explicit on ecological components. The studies demonstrate the livelihood benefits to all of the interventions and significant variation in achievements with reference to sustainability, equity and democratic decentralization depending on the level and extent of community participation apart from the vision of implementers, strategy (or nature of intervention shaped by the question of community formation), the centrality of community formation and also the State policy. Case studies show that the influence of State policy is multi-faceted and often contradictory in nature. This necessitates NGOs to engage with the State in a much more purposeful way than in an ‘autonomous space’. Thus the role of NGOs in CBNRM is complementary, wherein they provide innovative experiments that the State can learn. This helps in achieving the goals of CBNRM through democratic decentralization. The book addresses the vital issues related to natural resource management and interests of the community. Key topics discussed throughout the book are still at the centre of the current debate. This compilation consists of well-written chapters based on rigorous synthesis of CBNRM case studies, which will serve as good references for students, researchers and practitioners in the years to come.

A Profilometric Approach to 3D Face Reconstruction and Its Application to Face Recognition

3D Face Recognition is an active area of research for past several years. For a 3D face recognition system one would like to have an accurate as well as low cost setup for constructing 3D face model. In this paper, we use Profilometry approach to obtain a 3D face model.This method gives a low cost solution to the problem of acquiring 3D data and the 3D face models generated by this method are sufficiently accurate. We also develop an algorithm that can use the 3D face model generated by the above method for the recognition purpose.

Optimal placement of Distributed Generation for a projected load increase using Relative Electrical Distance approach

There is a lot of pressure on all the developed and second world countries to produce low emission power and distributed generation (DG) is found to be one of the most viable ways to achieve this. DG generally makes use of renewable energy sources like wind, micro turbines, photovoltaic, etc., which produce power with minimum green house gas emissions. While installing a DG it is important to define its size and optimal location enabling minimum network expansion and line losses. In this paper, a methodology to locate the optimal site for a DG installation, with the objective to minimize the net transmission losses, is presented. The methodology is based on the concept of relative electrical distance (RED) between the DG and the load points. This approach will help to identify the new DG location(s), without the necessity to conduct repeated power flows. To validate this methodology case studies are carried out on a 20 node, 66kV system, a part of Karnataka Transco and results are presented.

Evaluation of isopentane, R-245fa and their mixtures as working fluids for organic Rankine cycles

Low grade thermal energy from sources such as solar, geothermal and industrial waste heat in the temperature range of 380-425 K can be converted to electrical energy with reasonable efficiency using isopentane and R-245fa. While the former is flammable and the latter has considerable global warming potential, their mixture in 0.7/0.3 mole fraction is shown to obviate these disadvantages and yet retain dominant merits of each fluid. A realistic thermodynamic analysis is carried out wherein the possible sources of irreversibilities such as isentropic efficiencies of the expander and the pump and entropy generation in the regenerator, boiler and condenser are accounted for. The performance of the system in the chosen range of heat source temperatures is evaluated. A technique of identifying the required source temperature for a given output of the plant and the maximum operating temperature of the working fluid is developed. This is based on the pinch point occurrence in the boiler and entropy generation in the boiling and superheating regions of the boiler. It is shown that cycle efficiencies of 10-13% can be obtained in the range investigated at an optimal expansion ratio of 7-10. (C) 2012 Elsevier Ltd. All rights reserved.

MAPS: midline analysis and propagation of segmentation

Scenic word images undergo degradations due to motion blur, uneven illumination, shadows and defocussing, which lead to difficulty in segmentation. As a result, the recognition results reported on the scenic word image datasets of ICDAR have been low. We introduce a novel technique, where we choose the middle row of the image as a sub-image and segment it first. Then, the labels from this segmented sub-image are used to propagate labels to other pixels in the image. This approach, which is unique and distinct from the existing methods, results in improved segmentation. Bayesian classification and Max-flow methods have been independently used for label propagation. This midline based approach limits the impact of degradations that happens to the image. The segmented text image is recognized using the trial version of Omnipage OCR. We have tested our method on ICDAR 2003 and ICDAR 2011 datasets. Our word recognition results of 64.5% and 71.6% are better than those of methods in the literature and also methods that competed in the Robust reading competition. Our method makes an implicit assumption that degradation is not present in the middle row.

Processing of DNA double-stranded breaks and intermediates of recombination and repair by saccharomyces cerevisiae Mre11 and its stimulation by Rad50, Xrs2, and Sae2 proteins

Saccharomyces cerevisiae RAD50, MRE11, and XRS2 genes are essential for telomere length maintenance, cell cycle checkpoint signaling, meiotic recombination, and DNA double-stranded break (DSB) repair via nonhomologous end joining and homologous recombination. The DSB repair pathways that draw upon Mre11-Rad50-Xrs2 subunits are complex, so their mechanistic features remain poorly understood. Moreover, the molecular basis of DSB end resection in yeast mre11-nuclease deficient mutants and Mre11 nuclease-independent activation of ATM in mammals remains unknown and adds a new dimension to many unanswered questions about the mechanism of DSB repair. Here, we demonstrate that S. cerevisiae Mre11 (ScMre11) exhibits higher binding affinity for single-over double-stranded DNA and intermediates of recombination and repair and catalyzes robust unwinding of substrates possessing a 3' single-stranded DNA overhang but not of 5' overhangs or blunt-ended DNA fragments. Additional evidence disclosed that ScMre11 nuclease activity is dispensable for its DNA binding and unwinding activity, thus uncovering the molecular basis underlying DSB end processing in mre11 nuclease deficient mutants. Significantly, Rad50, Xrs2, and Sae2 potentiate the DNA unwinding activity of Mre11, thus underscoring functional interaction among the components of DSB end repair machinery. Our results also show that ScMre11 by itself binds to DSB ends, then promotes end bridging of duplex DNA, and directly interacts with Sae2. We discuss the implications of these results in the context of an alternative mechanism for DSB end processing and the generation of single-stranded DNA for DNA repair and homologous recombination.

Origin of enhanced photocatalytic activity and photoconduction in high aspect ratio ZnO nanorods

Faceted ZnO nanorods with different aspect ratios were synthesized by a solvothermal method by tuning the reaction time. Increased reaction leads to the formation of high aspect ratio ZnO nanorods largely bound by the prism planes. The high aspect ratio rods showed significantly higher visible light photocatalytic activity when compared to the lower aspect ratio structures. It is proposed that the higher activity is due to better charge separation in the elongated 1D structure. In addition, the fraction of unsaturated Zn2+ sites is higher on the {10 (1) over bar0} facets, leading to better adsorption of oxygen-containing species. These species enhance the production of reactive radicals that are responsible for photodegradation. The photocurrent for these ZnO nanostructures under solar light was measured and a direct correlation between photocurrent and aspect ratio was observed. Since the underlying mechanisms for photodegradation and photocurrent generation are directly related to the efficiency of electron-hole creation and separation, this observation corroborates that the charge separation processes are indeed enhanced in the high aspect ratio structures. The efficiency of photoconduction (electron-hole pair separation) could be further improved by attaching Au nanoparticles on ZnO, which can act as a sink for the electrons. This heterostructure exhibits a high chemisorption of oxygen, which facilitates the production of highly reactive radicals contributing to the high photoreactivity. The suggested mechanisms are applicable to other n-type semiconductor nanostructures with important implications for applications relating to energy and the environment.

Comparison of CO2 and steam in transcritical Rankine cycles for concentrated solar power

High temperature, high pressure transcritical condensing CO2 cycle (TC-CO2) is compared with transcritical steam (TC-steam) cycle. Performance indicators such as thermal efficiency, volumetric flow rates and entropy generation are used to analyze the power cycle wherein, irreversibilities in turbo-machinery and heat exchangers are taken into account. Although, both cycles yield comparable thermal efficiencies under identical operating conditions, TC-CO2 plant is significantly compact compared to a TC-steam plant. Large specific volume of steam is responsible for a bulky system. It is also found that the performance of a TC-CO2 cycle is less sensitive to source temperature variations, which is an important requirement of a solar thermal system. In addition, issues like wet expansion in turbine and vacuum in condenser are absent in case of a TC-CO2 cycle. External heat addition to working fluid is assumed to take place through a heat transfer fluid (HTF) which receives heat from a solar receiver. A TC-CO2 system receives heat though a single HTF loop, whereas, for TC-steam cycle two HTF loops in series are proposed to avoid high temperature differential between the steam and HTF. (C) 2013 P. Garg. Published by Elsevier Ltd.