Abstract

Macrocyclic trienes are important precursors for the synthesis of several biologically relevant molecules such as steroids. These molecules undergo (4+2) cycloaddition to form tricyclic compounds, which has four newly formed stereocenters. The stereochemistry at these four carbon centers has been shown to be largely controlled by the reaction energy barriers, and the conformational preferences of the macrocycle. Molecular dynamics (MD) simulation is a highly efficient approach for studying conformational properties of chemical molecules and biological macromolecules. MP2/6-31G* method was used to obtain potential energy surfaces corresponding to appropriate model compounds and used as the target data. The force field parameters were refined to accurately represent the target data involving all the model compounds chosen. Using the refined molecular mechanics force field, MD simulations were performed on six possible 14-membered symmetric trienes at different temperatures. We have also used replica exchange MD (RexMD) simulations with eight replicas between 300 and 370 K. The molecules were found to sample a larger conformational space in the RexMD simulation compared to the regular MD simulations. The probability distributions corresponding to the dihedral angles, and distances between the reaction centers have been analyzed. The relationship between the conformational sampling of the macrocyclic trienes vis-à-vis their reactivity will be discussed. Additionally, clustering of the structures from the MD trajectories was done to identify all unique conformations using a new approach.

Abstract

Peptides incorporating 5 membered rings such as furan and tetrahydrofuran (THF) adopt secondary folding patterns and thus mimic natural peptides. The preferred conformation of linear and cyclized peptides incorporating sugar amino acids depends on the stereochemistry of at the chiral center. Control of stereochemistry of THF amino acid (TAA) in the structure of the linear tripeptide Boc-TAA-Leu-Val-OMe containing (2R,5S)-cis TAA, (2S,5R)-cis TAA, (2R,5R)-trans TAA and (2S,5S)-trans TAA is investigated using structural parameters and energetics data obtained from density functional theory (DFT) based calculations at B3LYP/6-31G(d,p) level of theory. We found that the conformations associated with -, - turn structures are stabilized by intramolecular hydrogen bonding interactions. Kinetic control of reactions leading to intra and inter molecular cyclization of tripeptide TAA-Gly-Gly containing (2S,5R)-cis TAA and (2S,5S)-trans TAA is studied at the same level of theory in gas phase[1]. We observe that kinetic control favors cyclodimerization instead of intramolecular cyclization. Theoretical study of reactions leading to linear and cyclic trimerization of backbone altered -peptide, i. e., amino ethyl furan carboxylic acid (AEFC) at the same level of theory have revealed the role of stereochemistry at C position of AEFC in the preferential formation of asymmetric RRS cyclic tripeptide formed by R-, R- and S- stereo isomers of AEFC.

Abstract

Forests are depleted drastically at higher rates to cope up the needs of increasing population. The present study was carried out to assess the impact of anthropogenic and natural disturbances (tsunami) on the vegetation of North Andaman islands using three different satellite images of different time period by visual image interpretation technique. A higher proportion of land cover and vegetation converted into agriculture, settlement, sand and water. Assessment of overall forest change from 1976 to 2005 is 117 Km 2 , with forest loss at the rate of 3.8 Km 2 / year. Simulation study for future forest scenario predicted an increase in agriculture / settlement area to be 196, 296, 392 and 492 Km 2 for the next 25, 50, 75 and 100 years, coupled with the conversion of forest areas of 131, 227, 320 and 427 Km 2 . Finally by the end of 100 years the estimated forest area of 1271 Km 2 (1999 data) reduces to 846 Km 2 if proper conservative actions are not taken.

Abstract

Water bodies, the aquatic systems on land, are one of the important store houses for variety of wildlife as well as nesting and breeding sites for different kind of avifauna. Currently these water bodies are under tremendous human pressure due to rapid urbanization. The lakes and reservoirs, across the country, are in varying degrees of environmental degradation due to various anthropogenic activities. In this context a study was carried out in and around the city, covering an area of about 7800 km2 to identify the impact of expanding urbanization process on water bodies of the Hyderabad city using 1989 and 2001 satellite data. The results of the study showed reduction in water bodies both in the area (19%) as well as in number. A negative change was observed in the status of water bodies towards NE and NW directions of the city. Most of the water bodies either were encroached by urban expansion or reduced in size due to eutrophication process. The expanding IT sector and developments in real estate, acted as major driving forces that converted agricultural lands into residential plots and there by exerting pressure on the nearby water bodies. The change study here provides us with vital clues towards understanding the change in water bodies’ vis-à-vis the urban needs, economic growth, and its location characteristics within a rapidly urbanization region.

Abstract

We solve instances of a general class of problems de- ned as follows: Preprocess a set S of possibly weighted colored geometric objects (e.g. points/orthogonal seg- ments/rectangles) in Rd, d  1 such that given a query orthogonal range q, we can report eciently for each dis- tinct color c of the points in S \q, the tuple < c;F(c) > where F(c) is a function (e.g. weighted sum, bounding box etc.) of the objects of color c in q.

Abstract

Automatic object extraction from urban areas using high resolution satellite images remains an open research area. High variability in object features like color, shape and scale makes the urban scene classification challenging. Though significant amount of work has been done on detecting buildings, roads and other objects individually, not much work is present for complete urban scene classification. This paper proposes an algorithm that makes use of color as an important cue along with geometry and shadow information for complete urban scene classification.

Abstract

Autism and dyslexia are both developmental disorders of neural origin. As we still do not understand the neural basis of these disorders fully, technology can take two approaches in helping those affected. The first is to compensate externally for a known difficulty and the other is to achieve the same function using a completely different means. To demonstrate the first option, we are developing a system to compensate for the auditory processing difficulties in case of dyslexia and to demonstrate the second option we propose a system for autism where we remove the need for traditional languages and instead use pictures for communication.

Abstract

The high level of engagement students have with games has motivated many researches to study various aspect of games-based learning. The approach taken in most of the studies is bringing instruction element implicitly in games. Adapting instructional content for creating games is a viable alternative approach to create interactive virtual learning environment development. Pedagogical support in the form of simulation exercises have been shown to be more effective in learning context. In this paper we argue the simulation exercises can be combined to produce games using an authoring tool. We illustrate our idea with an exemplar in the form of a 3D virtual physics game authoring tool. The results of evaluation of our exemplar indicate that use of subject-related terminology can help participants relate virtual game context with theoretical and real world phenomenon; however, games by themselves may not serve to be an effective way to learn new concepts.

Abstract

Mathematics is one of the difficult subjects children encounter. This is attributed to the fact that mathematics is taught as an abstract set of symbols and rules. Many innovative approaches have been tried to clear this misconception and make children see the real applications of mathematics. One such approach is using ethnomathematics – the mathematics present in the cultural forms of an ethnic group. In this work, we explore the effectiveness of this approach to teach a difficult mathematics concept – fractions. Fractions have been chosen due to its complexity and the inherent difficulties they pose to children. A tool was developed to teach fractions by engaging the child in two activities – making a bead necklace and tiling an area. The evaluation results indicate that such an approach is very effective in teaching the concept.

Abstract

Exudates are a class of lipid retinal lesions visible through optical fundus imaging, and indicative of diabetic retinopathy. We propose a clustering-based method to segment exudates, using multi-space clustering, and colorspace features. The method was evaluated on a set of 89 images from a publicly available dataset, and achieves an accuracy of 89.7% and positive predictive value of 87%.