Design and synthesis of new monoterpenoid derived ligands for asymmetric catalysis /

The work to be presented herein illustrates several important facts. First, the synthesis of BIBOL (19), a 1,4-diol derived from the monoterpene camphor has allowed us to demonstrate that oxidative dimerizations of enolates can, and do proceed with nearly complete diastereoselectivity under kinetically controlled conditions. The yield of BIBOL is now 50% on average, with a 10% yield of a second diastereomer, which is likely the result of a non-kinetic hydride reduction, thereby affording the epimeric alcohol, 20, coupled on the exo face of camphor. This implies the production of 60% of a single coupling diastereomer. No other diastereomers from the reduction were observed. The utility of BEBOL has been illustrated in early asymmetric additions of diethylzinc to aryl aldehydes, with e.e.'s as high as 25-30%. '^' To further the oxidative coupling work, the same methodology which gave rise to BIBOL was applied to the chiral pool ketone, menthone. Interestingly, this gave an excellent yield of the a-halohydrin (31), which is the result of a chlorination of menthone. This result clearly indicates the high stereoselectivity of the process regardless of the outcome, and has illustrated an interesting dichotomy between camphor and menthone. The utility of the chlorination product as a precursor other chiral ligands is currently being investigated. > ' Finally, a new series of 1,3-diols as well as a new aminoalcohol have successfully been synthesized from highly diastereoselective aldol/mannich reactions. Early studies have indicated their potential in asymmetric catalysis, while employing pi-stack interactions as a means of controlling enantioselective aldol reactions.

The cloning and reconstitution of a bovine adenovirus type 2 E3 deletion mutant and the sequencing and analysis of the early 4 region

Recombinant Adenoviruses (Ads) have been shown to have potential applications in three areas: gene therapy, high level protein expression and recombinant vaccines.' At least three different locations within the Ad genome can be deleted and subsequently used for the insertion of foreign sequences. These include the Early 3 (E3), Early 1 (E1) and Early 4 (E4) regions. Viral vectors of this type have been well studied in Human Ads 2 and 5, however one has not yet been constructed for Bovine Adenovirus Type 2 (BAV2). The E3 region is located between 76.6 and 86 m.u. on the r-strand and is transcribed in a rightward direction. The gene products of the Early 3 region (E3) have been shown to be non-essential for viral replication, in vitro, but are required for host immunosurveillance. This study represents the cloning and reconstitution of a BAV2 E3 deletion mutant. A deletion of 1800bp was made within the E3 region of BAV2 and the thymidine kinase gene was subsequently inserted in the deleted area . . The plasmid pdlE3-4tk1 (23.4Kbp) was constructed and used to to facilitate homologous recombination with the wild type BAV2 to produce a mutant. Southern Blotting and Hybridization results suggest the presence of a BAV2 E3 deletion mutant with thymidine kinase sequences present. The E4 region of Human Adenovirus types 2 and 5 is located at the extreme right end of the genome (91.3 map units - 99.1 map units) and is transcribed in a leftward direction giving rise to a complicated set of differentially spliced mRNAs. Essentially there are 7 open reading frames (ORFs) encoding for at least 7 polypeptides. The gene products encoded by the E4 region have been shown to be essential for the expression of late viral genes, host cell shutoff and normal viral growth. We have cloned and sequenced the right end segment between 90.5 map units and 100 map units of the BAV2 genome. The results show several open reading frames which encode polypeptides exhibiting homology to three polypeptides encoded by the E4 region of human adenovirus type 2. These include the 14kDa protein encoded by ORF1, the 34kDa protein encoded by ORF6 and the 13kDa protein encoded by ORF3. The nucleotide sequence, restriction enzyme map, and ORF map of the E4 region could be very useful in future molecular manipulation of this region and could possibly explain the slow growth rate of BAV2 in MDBK cells.

Isolation and analysis of a corprinus cinereus DNA fragment showing homology to a fimbrial cDNA from ustilago violacea

Surface proteinaceous fibrils, termed fimbriae, were first identified on gram negative bacteria in the 1940s. Fungal fimbriae, discovered some 25 years later, are found on members of all fungal classes. In the present study, polyclonal antiserum raised against the fimbrial proteins of U. vio/acea were used in order to identify antigenically related proteins from Coprinus cinereus and Schizophy//um commune. Two polypeptides with molecular masses of 37 and 39 kDa from C. cinereus were observed and confirm earlier results. A single previously unidentified 50 kDa polypeptide in S. commune crossreacted with the antiserum. The 50 kDa protein was found to consist of 3 isoforms with isoelectric points ranging from 5.6 to 5.8. A fimbrial cDNA derived from U. vio/acea was used to identify DNA restriction fragments from C. cinereus and S. commune showing homology to the fimbrial transcript of U. vio/acea. Heterologous hybridization with this cDNA was used in order to screen a C. cinereus genomic DNA library. A single clone, A2-3A, with a 14 kbp insert showed strong homology to the pfim3-1 cDNA. The region of homology, a 700 bp Xba I fragment, was subcloned into pUG19. This plasmid was refered to as pXX8. DNA sequence determinations of pXX8 and adjacent fragments from A2-3A suggested that the cloned DNA was a portion of the rONA repeat encoding the small subunit rRNA. DNA sequence analysis of pfim3-1 yielded an incomplete open reading frame. The predicted amino acid sequence codes for a 206 amino acid, 22 kDa polypeptide which contains a domain similar to a transmembrane domain from rat leukocyte antigen, GDS3. As well, an untranslated 576 nucleotide domain showed 81 % homology to pXX8 and 830/0 homology to the 188 rRNA sequence of Ustilago maydis. This sequence was found adjacent to a region of adenine-thymine base pairs presumed to represent the polyadenylation sequence of the fimbrial transcript. The size and extent of homology is sufficient to account for the hybridization of pfim3-1 to rDNA. It is suggested that this domain represents a completely novel regulatory domain within eukaryotes that may enable the observed rapid regeneration of fimbriae in U. violacea.

A multidimensional measurement approach and analysis of children's motivation for reading, attributional style, and reading achievement

The present study investigates the usefulness of a multi-method approach to the measurement of reading motivation and achievement. A sample of 127 elementary and middle-school children aged 10 to 14 responded to measures of motivation, attributions, and achievement both longitudinally and in a challenging reading context. Novel measures of motivation and attributions were constructed, validated, and utilized to examine the relationship between ~ motivation, attributions, and achievement over a one-year period (Study I). The impact of classroom contexts and instructional practices was also explored through a study of the influence of topic interest and challenge on motivation, attributions, and persistence (Study II), as well as through interviews with children regarding motivation and reading in the classroom (Study III). Creation and validation of novel measures of motivation and attributions supported the use of a self-report measure of motivation in situation-specific contexts, and confirmed a three-factor structure of attributions for reading performance in both hypothetical and situation-specific contexts. A one-year follow up study of children's motivation and reading achievement demonstrated declines in all components of motivation beginning at age 10 through 12, and particularly strong decreases in motivation with the transition to middle school. Past perceived competence for reading predicted current achievement after controlling for past achievement, and showed the strongest relationships with reading-related skills in both elementary and middle school. Motivation and attributions were strongly related, and children with higher motivation Fulmer III displayed more adaptive attributions for reading success and failure. In the context of a developmentally inappropriate challenging reading task, children's motivation for reading, especially in terms of perceived competence, was threatened. However, interest in the story buffered some ofthe negative impacts of challenge, sustaining children's motivation, adaptive attributions, and reading persistence. Finally, children's responses during interviews outlined several emotions, perceptions, and aspects of reading tasks and contexts that influence reading motivation and achievement. Findings revealed that children with comparable motivation and achievement profiles respond in a similar way to particular reading situations, such as excessive challenge, but also that motivation is dynamic and individualistic and can change over time and across contexts. Overall, the present study outlines the importance of motivation and adaptive attributions for reading success, and the necessity of integrating various methodologies to study the dynamic construct of achievement motivation.

Pointers on Design and Operation of Cattle Restrainer Systems

The article discusses the importance of design and the people who run handling systems.

The Design and Construction of Facilities for Handling Cattle

The article focuses on the following: Cattle Perception, How to prevent Balking, Solid Fences, Flight Zone, Curved Race more Efficient, Curved Race and Crowd Pen Dimensions, Loading Ramps, Working Corral for a Large Ranch, Squeeze Chutes and Headgates, Calf Tables, Artificial Insemination Chute, New Restraint Ideas, Dipping Vats, Bruise and Injury Prevention, Washable Facilities.

Computation and Analysis of Multiple Structural-Change Models

In a recent paper, Bai and Perron (1998) considered theoretical issues related to the limiting distribution of estimators and test statistics in the linear model with multiple structural changes. In this companion paper, we consider practical issues for the empirical applications of the procedures. We first address the problem of estimation of the break dates and present an efficient algorithm to obtain global minimizers of the sum of squared residuals. This algorithm is based on the principle of dynamic programming and requires at most least-squares operations of order O(T 2) for any number of breaks. Our method can be applied to both pure and partial structural-change models. Secondly, we consider the problem of forming confidence intervals for the break dates under various hypotheses about the structure of the data and the errors across segments. Third, we address the issue of testing for structural changes under very general conditions on the data and the errors. Fourth, we address the issue of estimating the number of breaks. We present simulation results pertaining to the behavior of the estimators and tests in finite samples. Finally, a few empirical applications are presented to illustrate the usefulness of the procedures. All methods discussed are implemented in a GAUSS program available upon request for non-profit academic use.

Modelling and Analysis of Some Time Series

The thesis deals with some of the non-linear Gaussian and non-Gaussian time models and mainly concentrated in studying the properties and application of a first order autoregressive process with Cauchy marginal distribution. In this thesis some of the non-linear Gaussian and non-Gaussian time series models and mainly concentrated in studying the properties and application of a order autoregressive process with Cauchy marginal distribution. Time series relating to prices, consumptions, money in circulation, bank deposits and bank clearing, sales and profit in a departmental store, national income and foreign exchange reserves, prices and dividend of shares in a stock exchange etc. are examples of economic and business time series. The thesis discuses the application of a threshold autoregressive(TAR) model, try to fit this model to a time series data. Another important non-linear model is the ARCH model, and the third model is the TARCH model. The main objective here is to identify an appropriate model to a given set of data. The data considered are the daily coconut oil prices for a period of three years. Since it is a price data the consecutive prices may not be independent and hence a time series based model is more appropriate. In this study the properties like ergodicity, mixing property and time reversibility and also various estimation procedures used to estimate the unknown parameters of the process.

Design and Development of a Performance Evaluation Prototype for IT Organizations in the Context of Outsourcing

The present study shows design and development of a performance evaluation prototype for IT organizations in the context of outsourcing. The main objective of this research is to help an IT organization in the context of outsourcing to realize its current standing, so it can take corrective steps where ever necessary and strive for continuous improvement. Service level management (SLM) process plays a crucial role in controlling the quality provision for IT service. Out sourcing is the process of entrusting the responsibility of providing certain goods and services to an external party. We have tried to identify as many as twenty complexities and categorized in to four headings. Complexities associated with contracts and SLAs,SLM process,SLM organization and complexities due to intrinsic characteristics. In this study it is possible to measure the quality of the performance of an IT organization in an outsourcing environment effectively

DESIGN AND DEVELOPMENT OF COMPACT ASYMMETRIC COPLANAR STRIP FED ANTENNAS

Antennas are indispensable component of any wireless communication device. An antenna is a transducer between the transmitter and the free space waves and vice versa. They efficiently transfer electromagnetic energy from a transmission line into free space. But the present day communication applications require compact and ultra wide band designs which cannot be catered by simple microstrip based designs. PIFAs have solved the problem to some extend, but the field of antennas needs more innovative designs In this thesis the design and development of compact planner antenna are presented. Emphasis is given to the design of the feed as well as the radiator resulting in simple compact uniplanar geometries. The Asymmetric coplanar feed used to excite the antennas is found to be a suitable choice for feeding compact antennas.The main objectives of the study are the design of compact single, dual and multi band antennas with uniplanar structure and extension of the design for practical GSM/WLAN applications and Ultra compact antennas using the above techniques and extension of the design to antennas for practical applications like RFID/DVB-H. All the above objectives are thoroughly studied. Antennas with ultra compact dimensions are obtained as a result of the study. Simple equations are provided to design antennas with the required characteristics. The design equations are verified by designing different antennas for different applications.

Development And Analysis Of A Compact Coplanar Antenna With Flared Monopole For Dual Band Applications

Department of Electronics, Cochin University of Science and Technology

DEVELOPMENT AND ANALYSIS OF DUAL FREQUENCY MICROSTRIP ANTENNAS

Department of Elecctronics, Cochin University of Science and Technology

Development and Analysis of a Drum-Shaped Compact Microstrip Antenna

The thesis is the outcome of the experimental and theoretical investigations on a new compact drum-shaped microstrip antenna. A new compact antenna suitable for personal communication system(PCS), Global position System(GPS) and array applications is developed and analysed. The generalised cavity model and spatial fourier transform technique are suitably modified for the analysis of the antenna. The predicted results are compared with experimental results and excellent agreement is observed. The experimental work done by the author in related fields are incorporated as three appendices in this thesis. A single feed dual frequency microstrip antenne is presented in appendix A.Appendix B describes a new broadband dual frequeny microstrip antenna. The bandwidth enhancement effect of microstrip antennas through dielectric resonator loading is demonstarted in Appendix C.