Conformational flexibility of DNA: polymorphism and handedness

It is shown that left-handed duplexes are possible for A, B, and D forms of DNA. These duplexes are stereochemically satisfactory and are consistent with the observed x-ray intensity data. On scrutiny the refined right-handed models of B and D DNA by Arnott and coworkers are found to be stereochemically unacceptable. It was possible to formulate a stereochemical guideline for molecular model building based on theory and analysis of single-crystal structure data of dinucleoside monophosphate and higher oligomers. This led to both right- and left-handed DNA duplexes. The right-handed B and D DNA duplexes so obtained are stereochemically superior to earlier models and agree well with the observed x-ray intensity data. The observation that DNA can exist in either handedness for all the polymorphous forms of DNA at once explained A in equilibrium B and B in equilibrium D transitions. Hence it is confirmed that polymorphism of DNA is a reflection on the conformational flexibility inherent in DNA, the same cause that ultimately allows DNA in either handedness. The possibility of various types of right- and left-handed duplexes generated by using dinucleoside monophosphate and trinucleoside diphosphate as repeating units resulted in a variety of models, called RL models. All these models have alternating right and left helical segments and inverted stacking at the bend region as suggested by us earlier. It turns out that the B-Z DNA model of Wang et al. is only an example of RL models.

Cultural-Evolution of Ecological Prudence

Animals often behave in a profligate fashion and decimate the populations of plants and animals they depend upon. They may, however, evolve prudent behaviour under special conditions, namely when such prudence greatly enhances the success of populations that are not too prone to invasions by profligate individuals. Cultural evolution in human societies can also lead to the adoption of prudent practices under similar conditions. These are more likely to be realized in stable environments in which the human populations tend to grow close to the carrying capacity, when the human groups are closed, and when the technology is stagnant. These conditions probably prevailed in the hunter—gatherer societies of the tropics and subtropics, and led to the adoption of a number of socially imposed restraints on the use of plant and animal resources. Such practices were rationalized in the form of Nature-worship. The Indian caste society became so organized as to fulfill these conditions, and gave rise to two religions, Buddhism and Jainism, which emphasize compassion towards all forms of life. The pastoral nomads of the middle east, on the other hand, lived in an environment which militated against prudence, and these societies gave rise to religions like Christianity, which declared war on nature. As the ruling elite and state have grown in power, they have tried to wrest control of natural resources from the local communities. This has sometimes resulted in conservation and prudent use under guidance from the state, but has often led to conflicts with local populations to the detriment of prudent behaviour. Modern technological progress has also often removed the need for conservation, as when availability of coal permitted the deforestation of England. While modern scientific understanding has led to a better appreciation of the need for prudence, the prevailing social and economic conditions often militate against any implementation of the understanding, as is seen from the history of whaling. However, the imperative for survival of the poor from the Third-World countries may finally bring about conditions in which ecological prudence may once again come to dominate human cultures as it might once have done with stable societies of hunter—gatherers.

Asymptotic behaviour of point processes with Markov-dependent intervals

This splitting techniques for MARKOV chains developed by NUMMELIN (1978a) and ATHREYA and NEY (1978b) are used to derive an imbedded renewal process in WOLD's point process with MARKOV-correlated intervals. This leads to a simple proof of renewal theorems for such processes. In particular, a key renewal theorem is proved, from which analogues to both BLACKWELL's and BREIMAN's forms of the renewal theorem can be deduced.

The Origin of Regioselectivity in a-Cleavage Reactions of Cyclopropenethiones: Potential Role of Pseudo-Jahn-Teller Effect in Substituted Cyclopropenyl Systems

Arylalkylcyclopropenethiones undergo highly regioselective photochemical a-cleavage via thioketene carbene intermediates, giving rise to products derived from the less stabilized carbene. UHF MIND0/3 calculations provide an insight into this unexpected regioselectivity. The nx* triplet of cyclopropenethione is calculated to have a highly unsymmetrical geometry with an elongated C-C bond, a delocalized thiaaUyl fragment, and a pyramidal radicaloid carbon (which eventually becomes the carbene center). From this molecular electronic structure, aryl group stabilization is expected to be more effective at the thiaallyl group rather than at the pyramidal radical center. Thus, the stability of the substituted triplet thione rather than that of the thioketene carbene determines the preferred regiochemistry of cleavage. The unusual structure of the cyclopropenethione triplet is suggested to be related to one of the Jahn-Teller distorted forms of the cyclopropenyl radical. An alternative symmetrical structure is adopted by the corresponding triplet of cyclopropenone, partly accounting for its differing photobehavior. A similar structural dichotomy is demonstrated for the corresponding radical anions as well.

Pressure dependence of 35Cl NQR in hexachloro- (N3P3Cl6) and octachloro- (N4P4Cl8) cyclophosphazenes

High pressure studies of 35Cl NQR in the hexachlorocyclophosphazene N3P3Cl6 and in the K- and T-forms of octachlorocyclophospha.

An infrared spectroscopic study of the phase transitions of crystalline aromatic donor-acceptor complexes involving a pseudoplastic state

Variable temperature i.r. spectroscopic studies of weak pi-donor-pi-acceptor complexes in the crystalline state indicate that the complexes undergo order-disorder transitions, the disorder being caused by molecular motion. Thermodynamic data on the phase transitions along with the spectral data suggest that the high-temperature crystalline forms of the complexes are likely to be pseudoplastic.

Crystallographic and modelling studies on Mycobacterium tuberculosis RuvA: Additional role of RuvB-binding domain and inter species variability

RuvA, along with RuvB, is involved in branch migration of heteroduplex DNA in homologous recombination. The structures of three new crystal forms of RuvA from Mycobacterium tuberculosis (MtRuvA) have been determined. The RuvB-binding domain is cleaved off in one of them. Detailed models of the complexes of octameric RuvA from different species with the Holliday junction have also been constructed. A thorough examination of the structures presented here and those reported earlier brings to light the hitherto unappreciated role of the RuvB-binding domain in determining inter-domain orientation and oligomerization. These structures also permit an exploration of the interspecies variability of structural features such as oligomerization and the conformation of the loop that carries the acidic pin, in terms of amino acid substitutions. These models emphasize the additional role of the RuvB-binding domain in Holliday junction binding. This role along with its role in oligomerization could have important biological implications.