Form and Function of Proteins. Historical Background and the Indian Effort in Macromolecular Crystallography

Global efforts in macromolecular crystallography started in the thirties of the last century. However, definitive results began to emerge only in the late fifties and the early sixties. India has a long tradition in crystallography. The country had a head start in theoretical and computational structural biology, thanks to the efforts of G.N. Ramachandran and his colleagues in the fifties and the sixties. However, macromolecular crystallography got off the ground in India only in the eighties, particularly after the Bangalore group received adequate support from the Department of Science and Technology under their Thrust Area Programme. The Bangalore centre was also identified as a national nucleus for the development of the area in the country. Since then work in the area has spread widely and is being carried out by several groups, mainly led by scientists trained at Bangalore or their descendents, in about thirty institutions in India. In addition to the Department of Science and Technology, the effort is now supported by other agencies like the Department of Biotechnology and the Council of Scientific and Industrial Research. The problems addressed by macromolecular crystallographers in India encompass almost all aspects of modern biology. Indian efforts in macromolecular crystallography have also become an important component of the international efforts in the area.

Certain Aspects Related To Computation By Modified Crack Closure Integral(MCCI)

This paper presents the proper computational approach for the estimation of strain energy release rates by modified crack closure integral (MCCI). In particular, in the estimation of consistent nodal force vectors used in the MCCI expressions for quarter-point singular elements (wherein all the nodal force vectors participate in computation of strain energy release rates by MCCI). The numerical example of a centre crack tension specimen under uniform loading is presented to illustrate the approach.

Some aspects of multilevel load-frequency control of a power system

The application of multilevel control strategies for load-frequency control of interconnected power systems is assuming importance. A large multiarea power system may be viewed as an interconnection of several lower-order subsystems, with possible change of interconnection pattern during operation. The solution of the control problem involves the design of a set of local optimal controllers for the individual areas, in a completely decentralised environment, plus a global controller to provide the corrective signal to account for interconnection effects. A global controller, based on the least-square-error principle suggested by Siljak and Sundareshan, has been applied for the LFC problem. A more recent work utilises certain possible beneficial aspects of interconnection to permit more desirable system performances. The paper reports the application of the latter strategy to LFC of a two-area power system. The power-system model studied includes the effects of excitation system and governor controls. A comparison of the two strategies is also made.

Monoblock cylinder internally pressurised under asymmetric end constraints Some aspects of design

The finite element method is used to analyse stresses and displacements in a monoblock cylinder open at one end only. The cylinder is internally pressurised. The analysis shows that the minimum pressure required to cause yield in the cylinder decreases rapidly with increasing cylinder height until the height is about the same as the outer radius of the cylinder, beyond which the decrease is marginal. Introduction of a fillet at the internal corner enhances the design pressure substantially while a fillet at the outer corner affects this pressure only marginally.

Bismuth tungsten-oxide bronzes - a study of intergrowth phases and related aspects

Reaction of bismuth metal with WO$_3$ in the absence of oxygen yields interesting bronze-like phases. From analytical electron microscopy and X-ray photoelectron spectroscopy, the product phases are found to have the general composition Bi$_x$ WO$_3$ with bismuth in the 3+ state. Structural investigations made with high resolution electron micrscopy and cognate techniques reveal that when x < 0.02, a perovskite bronze is formed. When x $\geqslant$ 0.02, however, intergrowth tungsten bronzes (i.t.b.) containing varying widths of the WO$_3$ slab are formed, the lattice periodicity being in the range 2.3-5.1 nm in a direction perpendicular to the WO$_3$ slabs. Image-matching studies indicate that the bismuth atoms are in the tunnels of the hexagonal tungsten bronze (h.t.b.) strips and the h.t.b. strips always remain one-tunnel wide. Annealed samples show a satellite structure around the superlattice spots in the electron diffraction patterns, possibly owing to ordering of the bismuth atoms in the tunnels. The i.t.b. phases show recurrent intergrowths extending up to 100 nm in several crystals. The periodicity varies considerably within the same crystal wherever there is disordered intergrowth, but unit cell dimensions can be assigned from X-ray and electron diffraction patterns. The maximum value of x in the i.t.b. phases is ca. 0.07 and there is no evidence for the i.t.b. phase progressively giving way to the h.t.b. phase with increase in x. Hexagonal tungsten bronzes that contain bismuth with x up to 0.02 can be formed by starting from hexagonal WO$_3$, but the h.t.b. phase seems to be metastable. Optical, magnetic and electron transport properties of the i.t.b. phases have been measured and it appears that the electrons become itinerant when x > 0.05.

Photochemical Oxidation of Thioketones: Steric and Electronic Aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Reassessing the earthquake hazard in Kerala based on the historical and current seismicity

Given the lack of proper constraints in understanding earthquake mechanisms in the cratonic interiors and the general absence of good quality database, here we reassess the seismic hazard in the province of Kerala, a part of the aEuro cent stable continental interioraEuro cent, based on an improved historical and instrumental database. The temporal pattern of the current seismicity suggests that > 60% of the microtremors in Kerala occurs with a time lag after the peak rainfall, indicating that hydroseismicity may be a plausible model to explain the low-level seismicity in this region. Further, an increment in overall seismicity rate in the region in the recent years is explained as due to increased anthropogenic activities, which includes changes in hydrological pathways as a consequence of rapid landscape changes. Our analyses of the historical database eliminate a few events that are ascribed to this region; this exercise has also led to identification of a few events, not previously noted. The improved historical database essentially suggests that the central midland region is more prone to seismic activity compared to other parts of Kerala. This region appears to have generated larger number of significant earthquakes; the most prominent being the multiple events (doublets) of 1856 and 1953, whose magnitudes are comparable to that of the 2000/2001 (central Kerala) events. Occurrences of these historical events and the recent earthquakes, and the local geology indicative of pervasive faulting as shown by widely distributed pseudotachylite veins suggest that the NNW-SSE trending faults in central midland Kerala may host discrete potentially active sources that may be capable of generating light to moderate size earthquakes. The frequency of earthquakes in central Kerala evident from the historical database requires that the seismic codes stipulated for this region are made mandatory.

Photochemical oxidation of thio ketones: steric and electronic aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Chemical aspects of the hypergolic preignition reactions of some hybrid hypergols

A new class of solid compounds, viz., bisthiocarbonohydrazones and thiosemicarbazones, have been found to be hypergolic with fuming nitric acid. The observed ignition delays of these hypergols have been compared with those of the monothiocarbonohydrazones-nitric acid systems and explained in terms of the chemical reactions-neutralization, oxidation, and nitration-occurring in the preignition stage. p-Nitrobenzoic acid, benzoic acid, benzaldehyde, sulfur trioxide, nitrogen dioxide, and nitrogen have been isolated as preignition reaction intermediates in the mono- and bisbenzaldehydethiocarbonohydrazone-nitric acid systems. A scheme of reactions occurring in the preignition stage is proposed based on the formation of these products.

Some aspects of multilevel load-frequency control of a power system

The application of multilevel control strategies for load-frequency control of interconnected power systems is assuming importance. A large multiarea power system may be viewed as an interconnection of several lower-order subsystems, with possible change of interconnection pattern during operation. The solution of the control problem involves the design of a set of local optimal controllers for the individual areas, in a completely decentralised environment, plus a global controller to provide the corrective signal to account for interconnection effects. A global controller, based on the least-square-error principle suggested by Siljak and Sundareshan, has been applied for the LFC problem. A more recent work utilises certain possible beneficial aspects of interconnection to permit more desirable system performances. The paper reports the application of the latter strategy to LFC of a two-area power system. The power-system model studied includes the effects of excitation system and governor controls. A comparison of the two strategies is also made.

Aspects of tautomerism 9-solvolysis of normal and pseudo phthaloyl chlorides

Solvolysis of normal and pseudo phthaloyl chlorides in aqueous acetone and in aqueous dioxane has revealed that the former solvolyses about hundred-fold faster than the latter. Contrary to the accepted belief, there is no evidence for equilibrium between the normal and the pseudo forms of phthaloyl chloride, under a variety of conditions.

Studies of phosphazenes. 28. Reactions of pentachloro- and pentafluoro(triphenylphosphazenyl)cyclotriphosphazenes with sodium methoxide. Mechanistic aspects and their implications for nucleophilic displacement at a tetrahedral phosphorus(V) center

Abstract is not available.

Aspects of tautomerism. 13. Alkaline hydrolysis of .gamma.-, .delta.-, and .epsilon.-keto esters and their desoxy analogs. Geometrical constraints on keto participation

The rates of alkaline hydrolysis of methyl &benzoylpropionate (I), methyl y-benzoylbutyrate (11) and methyll6-benzoylvalerate (In) decrease in the order I > I1 > III. Keto participation is the predominant pathway in the case of y-keto esters. Evidence has also been obtained for keto participation in the case of 6-keto esters, whereas no such evidence is available in the case of r-keto esters studied.

Oxidation of alkaline earth sulfides to sulfates: Thermodynamic aspects

The emf of the galvanic cell, Pt, Ni + NiO/(CaO) ZrO2/MS + MSO4, Ir, Pt, where M is calcium, strontium, or barium, has been measured in the temperature range 850 to 1100 K. From these measurements the Gibbs’ energy changes for the oxidation of sulfides of alkaline earth metals to their respective sulfates have been calculated. The results are compared with available thermodynamic data in the literature. The agreement varies from ±2 kJ for the strontium system to ±20 kJ in the case of barium. Trends in the stabilities of alkaline earth sulfates are discussed in relation to the properties of the cationic species involved.