Chemical synthesis of DNA and RNA containing thio-substituted bases and their post-synthetic modifications

Modified oligonucleotides containing sulphur group have been useful tools for studies of carcinogenesis, protein or nucleic acid structures and functions, protein-nucleic acid interactions, and for antisense modulation of gene expression. One successful example has been the synthesis and study of oligodeoxynucleotides containing 6-thio-2'-deoxyguanine. 6-Thio-2-deoxyguanosine was first discovered as metabolic compound of 6- mercaptopurine (6-MP). Later, it was applied as drug to cure leukaemia. During the research of its toxicity, a method was developed to use the sulphur group as a versatile position for post-synthetic modification. The advantage of application of post-synthetic modification lies in its convenience. Synthesis of oligomers with normal sequences has become routine work in most laboratories. However, design and synthesis of a proper phosphoramidite monomer for a new modified nucleoside are always difficult tasks even for a skilful chemist. Thus an alternative method (post-synthetic method) has been invented to overcome the difficulties. This was achieved by incorporation of versatile nucleotides into oligomers which contain a leaving group, that is sufficiently stable to withstand the conditions of synthesis but can be substituted by nucleophiles after synthesis, to produce, a series of oligomers each containing a different modified base. In the current project, a phosphoramidite monomer with 6-thioguanine has been successfully synthesised and incorporated into RNA. A deprotection procedure, which is specific for RNA was designed for oligomers containing 6-thioguanosine. The results were validated by various methods (UV, HPLC, enzymatic digestion). Pioneer work in utilization of the versatile sulphur group for post-synthetic modification was also tested. Post-synthetic modification was also carried out on DNA with 6- deoxythioguanosine. Electrophilic reagents with various functional groups (alphatic, aromatic, fluorescent) and bi-functional groups have been attached with the oligomers.

Lithological mapping of Northwest Argentina with remote sensing data using tonal, textural and contextual features

Tonal, textural and contextual properties are used in manual photointerpretation of remotely sensed data. This study has used these three attributes to produce a lithological map of semi arid northwest Argentina by semi automatic computer classification procedures of remotely sensed data. Three different types of satellite data were investigated, these were LANDSAT MSS, TM and SIR-A imagery. Supervised classification procedures using tonal features only produced poor classification results. LANDSAT MSS produced classification accuracies in the range of 40 to 60%, while accuracies of 50 to 70% were achieved using LANDSAT TM data. The addition of SIR-A data produced increases in the classification accuracy. The increased classification accuracy of TM over the MSS is because of the better discrimination of geological materials afforded by the middle infra red bands of the TM sensor. The maximum likelihood classifier consistently produced classification accuracies 10 to 15% higher than either the minimum distance to means or decision tree classifier, this improved accuracy was obtained at the cost of greatly increased processing time. A new type of classifier the spectral shape classifier, which is computationally as fast as a minimum distance to means classifier is described. However, the results for this classifier were disappointing, being lower in most cases than the minimum distance or decision tree procedures. The classification results using only tonal features were felt to be unacceptably poor, therefore textural attributes were investigated. Texture is an important attribute used by photogeologists to discriminate lithology. In the case of TM data, texture measures were found to increase the classification accuracy by up to 15%. However, in the case of the LANDSAT MSS data the use of texture measures did not provide any significant increase in the accuracy of classification. For TM data, it was found that second order texture, especially the SGLDM based measures, produced highest classification accuracy. Contextual post processing was found to increase classification accuracy and improve the visual appearance of classified output by removing isolated misclassified pixels which tend to clutter classified images. Simple contextual features, such as mode filters were found to out perform more complex features such as gravitational filter or minimal area replacement methods. Generally the larger the size of the filter, the greater the increase in the accuracy. Production rules were used to build a knowledge based system which used tonal and textural features to identify sedimentary lithologies in each of the two test sites. The knowledge based system was able to identify six out of ten lithologies correctly.

Inequality, fiscal capacity and the political regime: lessons from the post-communist transition

Using panel data for twenty-seven post-communist economies between 1987-2003, we examine the nexus of relationships between inequality, fiscal capacity (defined as the ability to raise taxes efficiently) and the political regime. Investigating the impact of political reform we find that full political freedom is associated with lower levels of income inequality. Under more oligarchic (authoritarian) regimes, the level of inequality is conditioned by the state’s fiscal capacity. Specifically, oligarchic regimes with more developed fiscal systems are able to defend the prevailing vested interests at a lower cost in terms of social injustice. This empirical finding is consistent with the model developed by Acemoglu (2006). We also find that transition countries undertaking early macroeconomic stabilisation now enjoy lower levels of inequality; we confirm that education fosters equality and the suggestion of Commander et al (1999) that larger countries are prone to higher levels of inequality.