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.

Ternary ion-pair complexation: a protocol for chiral discrimination and the assignment of absolute configuration of chiral hydroxy acids

The study demonstrates the utility of ternary ion-pair complex formed among BINOL (1,1'-Bi-2-naphthol), a carboxylic acid and an organic base, such as, dimethylpyridine (DMAP), 1,4-diazabicyclo2.2.2]octane (DABCO), as a versatile chiral solvating agent (CSA) for the enantiodiscrimination of carboxylic acids, measurement of enantiomeric excess (ee) and the assignment of absolute configuration of hydroxy acids. The proposed mechanism of ternary complex has wider application for testing the enantiopurity owing to the fact that the binary mixture using BINOL alone does not serve as a solvating agent for their discrimination. In addition, the developed protocol has an excellent utility for the assignment of the absolute configurations of hydroxy acids.

Performance Evaluation of OBS Networks with INI Signaling Technique

In this paper, we evaluate the performance of a burst retransmission method for an optical burst switched network with intermediate-node-initiation (INI) signaling technique. The proposed method tries to reduce the burst contention probability at the intermediate core nodes. We develop an analytical model to get the burst contention probability and burst loss probability for an optical burst switched network with intermediate-node-initiation signaling technique. The proposed method uses the optical burst retransmission method. We simulate the performance of the optical burst retransmission. Simulation results show that at low traffic loads the loss probability is low compared to the conventional burst retransmission in the OBS network. Result also show that the retransmission method for OBS network with intermediate-node-initiation signaling technique significantly reduces the burst loss probability.

Role of Crosslinking and Entanglements in the Mechanics of Silicone Networks

The goal of this study is to investigate the applicability of different constitutive models for silicone networks using comprehensive multiaxial experimental tests, including non-equibiaxial mechanical tests which introduce differential constraints on the networks in the two orthogonal directions, on samples prepared using various crosslinking densities. Uniaxial stress-strain experiments show that a decrease in crosslinker amounts used in the preparation of silicone networks lead to more compliant material response as compared to that obtained using higher amounts of crosslinker. Biaxial data were used to obtain fits to the neo- Hookean, Mooney-Rivlin, Arruda-Boyce and the Edward-Vilgis slip-link constitutive models. Our results show that the slip-link model, based on separation of the individual contributions of chemical crosslinks and physical entanglements, is better at describing the stress-strain response of highly crosslinked networks at low stretches as compared to other constitutive models. Modulus obtained using the slip-link model for highly crosslinked networks agrees with experimentally determined values obtained using uniaxial tension experiments. In contrast, moduli obtained using coefficients to the other constitutive models underpredict experimentally determined moduli by over 40 %. However, the slip-link model did not predict the experimentally observed stiffening response at higher stretches which was better captured using the Arruda-Boyce model.

Evolution of social behaviour in the primitively eusocial wasp Ropalidia marginata: do we need to look beyond kin selection?

Ropalidia marginata is a primitively eusocial wasp widely distributed in peninsular India. Although solitary females found a small proportion of nests, the vast majority of new nests are founded by small groups of females. In suchmultiple foundress nests, a single dominant female functions as the queen and lays eggs, while the rest function as sterile workers and care for the queen's brood. Previous attempts to understand the evolution of social behaviour and altruism in this species have employed inclusive fitness theory (kin selection) as a guiding framework. Although inclusive fitness theory is quite successful in explaining the high propensity of the wasps to found nests in groups, several features of their social organization suggest that forces other than kin selection may also have played a significant role in the evolution of this species. These features include lowering of genetic relatedness owing to polyandry and serial polygyny, nest foundation by unrelated individuals, acceptance of young non-nest-mates, a combination of well-developed nest-mate recognition and lack of intra-colony kin recognition, a combination of meek and docile queens and a decentralized self-organized work force, long reproductive queues with cryptic heir designates and conflict-free queen succession, all resulting in extreme intra-colony cooperation and inter-colony conflict.