Synthesis, Reactivity, Structural Aspects, and Solution Dynamics of Cyclopalladated Compounds of N,N `,N `'-Tris(2-anisyl)guanidine

N,N',N `'-Tris(2-anisyl)guanidine, (ArNH)(2)C=NAr (Ar = 2-(MeO)C6H4), was cyclopallaclated with Pd(OC(O)R)(2) (R = Me, CF3) in toluene at 70 degrees C to afford palladacycles Pd{kappa(2)(C,N)-C6H3-(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-OC(O)R)](2)(R = Me (1a) and CF3 (1b)) in 87% and 95% yield, respectively. Palladacycle 1a was subjected to a metathetical reaction with LiBr in aqueous ethanol at 78 degrees C to afford palladacycle Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (2) in 90% yield. Palladacycle 2 was subjected to a bridge-splitting reaction with Lewis bases in CH2Cl2 to afford the monomeric palladacycles Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}Br(L)] (L = 2,6-Me2C5H3N (3a), 2,4-Me2C5H3N (3b), 3,5-Me2C5H3N (3c), XyNC (Xy = 2,6-Me2C6H3; 4a), (BuNC)-Bu-t (4b), and PPh3 (5)) in 87-95% yield. Palladacycle 2 upon reaction with 2 equiv of XyNC in CH2Cl2 afforded an unanticipated palladacycle, Pd{kappa(2)(C,N)-C(=NXy)(C6H3(OMe)-4)-2(N=C-(NH Ar)(2))-3} Br(CNXy)] (6) in 93% yield, and the driving force for the formation of 6 was ascribed to a ring contraction followed by amine-imine tautomerization. Palladacycles 1 a,b revealed a dimeric transoid in-in conformation with ``open book'' framework in the solid state. In solution, 1 a exhibited a fluxional behavior ascribed to the six-membered ``(C,N)Pd'' ring inversion and partly dissociates to the pincer type and kappa(2)-O,O'-OAc monomeric palladacycles by an anchimerically assisted acetate cleavage process as studied by variable-temperature H-1 NMR data. Palladacycles 3a,b revealed a unique trans configuration around the palladium with lutidine being placed trans to the Pd-C bond, whereas cis stereochemistry was observed between the Pd-C bond and the Lewis base in 4a (as determined by X-ray diffraction data) and 5 (as determined by P-31 and C-13 NMR data). The aforementioned stereochemical difference was explained by invoking relative hardness/softness of the donor atoms around the palladium center. In solution, palladacycles 3a-c exist as a mixture of two interconverting boat conformers via a planar intermediate without any bond breaking due to the six-membered ``(C,N)Pd'' ring inversion, whereas palladacycles 4a,b and 5 exist as a single isomer, as deduced from detailed H-1 NMR studies.

Bioinorganic and medicinal chemistry: aspects of gold(I)-protein complexes

Gold(I)-based drugs have been used successfully for the treatment of rheumatoid arthritis (RA) for several years. Although the exact mechanism of action of these gold(I) drugs for RA has not been clearly established, the interaction of these compounds with mammalian enzymes has been extensively studied. In this paper, we describe the interaction of therapeutic gold(I) compounds with mammalian proteins that contain cysteine (Cys) and selenocysteine (Sec) residues. Owing to the higher affinity of gold(I) towards sulfur and selenium, gold(I) drugs rapidly react with the activated cysteine or selenocysteine residues of the enzymes to form protein-gold(I)-thiolate or protein-gold(I)-selenolate complexes. The formation of stable gold(I)-thiolate/selenolate complexes generally lead to inhibition of the enzyme activity. The gold-thiolate/selenolate complexes undergo extensive ligand exchange reactions with other nucleophiles and such ligand exchange reactions alter the inhibitory effects of gold(I) complexes. Therefore, the effect of gold(I) compounds on the enzymatic activity of cysteine-or selenocysteine-containing proteins may play important roles in RA. The interaction of gold(I) compounds with different enzymes and the biochemical mechanism underlying the inhibition of enzymatic activities may have broad medicinal implications for the treatment of RA.

Intraseasonal Variation of the Summer Monsoon I:Observational Aspects

Within the summer monsoon, the circulation and rainfall over the Indian region exhibit large variations over the synoptic scale of 3-7 days and the supersynoptic scales of 10 days and longer. In this paper we discuss some facets of intraseasonal variation on the supersynoptic scale on the basis of existing observational studies and some new analysis. The major variation of the summer monsoon rainfall on this scale is the active-break cycle. The deep convection over the Indian region on a typical day in the active phase is organized over thousands of kilometers in the zonal direction and is associated with a tropical convergence zone (TCZ). The intraseasonal variations on the supersynoptic scale are also coherent on these scales and are related to the space-time variation of the large-scale TCZ. The latitudinal distribution of the occurrence of the TCZ is bimodal with the primary mode over the heated continent and a secondary mode over the ocean. The variation of the continental TCZ is generally out of phase with that of the oceanic TCZ. During the active spells, the TCZ persists over the continent in the monsoon zone. The revival from breaks occurs either by northward propagation of the TCZ over the equatorial Indian Ocean or by genesis of a disturbance in the monsoon zone (often as a result of westward propagations from W. Pacific). The mechanisms governing the fluctuation between active spells and breaks, the interphase transition and the complex interactions of the TCZ over the Indian subcontinent with the TCZ over the equatorial Indian Ocean and the W. Pacific, have yet to be completely understood.

Some aspects of the solitary waves in a relativistic inhomogeneous plasma

In contrast to earlier observations on various solitary wave propagations, especially those bifurcated by the compressive and rarefactive solitary waves, the existence of spiky and explosive solitary waves is here believed to arise because of the presence of free and trapped electrons. So far, very few studies have been carried out to satisfactorily explain the presence of the solitary waves in space as observed by satellites. It is also attempted to highlight the probable impact on the various solitary wave propagations in a generalized multi-component, inhomogeneous plasma upon consideration of a relativistic treatment. It is expected that such a treatment will prove the existence of the solitary waves most expeditiously and exhibit the presence of chaos therein, thus giving a suitable explanation to the observations of various forms of spiky and explosive solitary waves in space-plasma. Copyright (C) 1996 Elsevier Science Ltd

Orientational disorder and other aspects of C70 and C60-C70 films deposited on single-crystal substrates

C-70 films deposited on highly oriented pyrolytic graphite (HOPG), Ag(110), Ag(111) and Pt(110) substrates have been investigated by scanning tunnelling microscopy. Interesting observations on novel molecular arrangements, as well as orientational disorder, are presented. Solid solutions of C-60 and C-70 show interesting packing of these molecules when deposited on HOPG.

Some aspects of information processing in biological vision

An attempt is made to present some challenging problems (mainly to the technically minded researchers) in the development of computational models for certain (visual) processes which are executed with, apparently, deceptive ease by the human visual system. However, in the interest of simplicity (and with a nonmathematical audience in mind), the presentation is almost completely devoid of mathematical formalism. Some of the findings in biological vision are presented in order to provoke some approaches to their computational models, The development of ideas is not complete, and the vast literature on biological and computational vision cannot be reviewed here. A related but rather specific aspect of computational vision (namely, detection of edges) has been discussed by Zucker, who brings out some of the difficulties experienced in the classical approaches.Space limitations here preclude any detailed analysis of even the elementary aspects of information processing in biological vision, However, the main purpose of the present paper is to highlight some of the fascinating problems in the frontier area of modelling mathematically the human vision system.

Some Basic Aspects of Reaction Engineering of Precipitation Processes

Analysis of precipitation reactions is extremely important in the technology of production of fine particles from the liquid phase. The control of composition and particle size in precipitation processes requires careful analysis of the several reactions that comprise the precipitation system. Since precipitation systems involve several, rapid ionic dissociation reactions among other slower ones, the faster reactions may be assumed to be nearly at equilibrium. However, the elimination of species, and the consequent reduction of the system of equations, is an aspect of analysis fraught with the possibility of subtle errors related to the violation of conservation principles. This paper shows how such errors may be avoided systematically by relying on the methods of linear algebra. Applications are demonstrated by analyzing the reactions leading to the precipitation of calcium carbonate in a stirred tank reactor as well as in a single emulsion drop. Sample calculations show that supersaturation dynamics can assume forms that can lead to subsequent dissolution of particles that have once been precipitated.

Phenomenological aspects of phase fluctuation in high Tc superconductors: Cooper pair droplets

We point out how fluctuation of the phase of the superconducting order parameter can play a key role in our understanding of high Te superconductors. A simple universal criterion is given which illustrates why all oxide superconductors in contrast to classical superconductors ought to behave as a lattice of cooper pairs. T-c is to be thought of as the temperature of phase coherence or the temperature above which the lattice of Cooperpair 'melts' into a phase of Cooper-pair droplets that starts forming at T approximate to T-* . This is the pseudo-gap region. Quantum fluctuation of the phase predicts a superconductor to insulator phase transition for all underdoped materials.

Some microbiological aspects of bauxite mineralization and beneficiation

A microbial survey of Jamnagar bauxite mines in Gujarat, India, revealed the indigenous presence of a variety of autotrophic and heterotrophic bacteria and fungi associated with the ore body and water ponds in the vicinity. Among these, bacteria belonging to the genera Thiobacillus, Bacillus and Pseudomonas are implicated in the weathering of aluminosilicates; the precipitation of iron oxyhydroxides; the dissolution and conversion of alkaline metal species; and the formation of alumina, silica and calcite minerals. Fungi belonging to the genus Cladosporium can reduce ferric iron and dissolve alumina silicates. Biogenesis thus plays a significant role in bauxite mineralization. Various types of bacteria and fungi, such as Bacillus polymyxa, Bacillus coagulans and Aspergillus niger, were found to be efficient in significant calcium solubilization and partial iron removal from bauxite ore. Probable mechanisms in the biobeneficiation process are analyzed. Biobeneficiation is shown to be an effective technique for the removal of iron and calcium from bauxite ores for use in refractories and ceramics.

Electrochemical aspects of leaching of ocean nodules in the presence and absence of microorganisms

instead of using chemical-reducing agents to facilitate the reduction and dissolution of manganese and iron oxide in the ocean nodule, electrochemical reduction based on two approaches, namely, cathodic polarization and galvanic interaction, can also be considered as attractive alternatives. Galvanic leaching of ocean nodules in the presence of pyrite and pyrolusite for complete recovery of Cu, Ni and Co has been discussed. The key for successful and efficient dissolution of copper, nickel and cobalt from ocean nodules depends on prior reduction of the manganese and ferric oxides with which the above valuable nonferrous metals are interlocked. Polarization studies using a slurry electrode system indicated that maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 mV (SCE) and -1400 mV (SCE). The present work is also relevant to galvanic bioleaching of ocean nodules using autotrophic microorganisms, such as Thiobacillus ferrooxidans and T thiooxidans, which resulted in significant dissolution of copper, nickel and cobalt at the expense of microbiologically generated acids. Various electrochemical and biochemical mechanisms are outlined and the electroleaching and galvanic processes so developed are shown to yield almost complete dissolution of all metal values. (C) 2002 Elsevier Science B.V. All rights reserved.

Certain Novel Aspects of Thallium and Bismuth Cuprate Superconductors

Novel superconducting thallium cuprates of the type T1Ca1‐X LnX Sr2 Cu2O6+δ (Ln = Y or rare earth), T1Srn+1‐x Lnx Cun OY and Tl1‐x PbX Srn+1Cun08+δ are described. These cuprates as well as Bi2Ca1‐x Lnx Sr2Cu2O8+δ and TICa1‐xYxBa2 Cu2 O6+δ . show maximum T around a specific composition or oxygen content. They also show interesting changes in the sign and magnitude of the thermopower with the composition. Specially noteworthy is the negative slope of the thermopower‐temperature plots. The thermopower behaviour in these two‐band systems can be understood in terms of entropie and quasiparticle contributions. It appears that Tl1‐x Pbx CaSr2Cu2O6+δ is a genuine high T electron superconductor.

Hyper-activation of the TCP4 transcription factor in Arabidopsis thaliana accelerates multiple aspects of plant maturation

Plant organs are initiated as primordial outgrowths, and require controlled cell division and differentiation to achieve their final size and shape. Superimposed on this is another developmental program that orchestrates the switch from vegetative to reproductive to senescence stages in the life cycle. These require sequential function of heterochronic regulators. Little is known regarding the coordination between organ and organismal growth in plants. The TCP gene family encodes transcription factors that control diverse developmental traits, and a subgroup of class II TCP genes regulate leaf morphogenesis. Absence of these genes results in large, crinkly leaves due to excess division, mainly at margins. It has been suggested that these class II TCPs modulate the spatio-temporal control of differentiation in a growing leaf, rather than regulating cell proliferation per se. However, the link between class II TCP action and cell growth has not been established. As loss-of-function mutants of individual TCP genes in Arabidopsis are not very informative due to gene redundancy, we generated a transgenic line that expressed a hyper-activated form of TCP4 in its endogenous expression domain. This resulted in premature onset of maturation and decreased cell proliferation, leading to much smaller leaves, with cup-shaped lamina in extreme cases. Further, the transgenic line initiated leaves faster than wild-type and underwent precocious reproductive maturation due to a shortened adult vegetative phase. Early senescence and severe fertility defects were also observed. Thus, hyper-activation of TCP4 revealed its role in determining the timing of crucial developmental events, both at the organ and organism level.