Interaction of synthetic analogs of distamycin and netropsin with nucleic acids. Does curvature of ligand play a role in distamycin-DNA interactions?

Distamycin and netropsin, a class of minor groove binding nonintercalating agents, are characterized by their B-DNA and A-T basespecific interactions. To understand the CQI I ~OIT~ ~ I ~ ~aOnMd ~c hemical basis of the above specificities, the DNA-binding characteristics of a novel synthetic analogue of distamycin have been studied. The analogue, mPD derivative, has the requisite charged end groups and a number of potential hydrogen-bonding loci equal to those of distamycin. The difference in the backbone curvatures of the ligands, distamycin, the mPD derivative, and NSC 101327 (another structurally analogous compound),is a major difference between these ligands. UV and CD spectrosoopic studies reported here show the following salient features: The mPD derivative recognizes only B-DNA, to which it binds via the minor groove. On the other hand, unlike distamycin, it binds with comparable affinities to A-T and G-C base pairs in a natural DNA. These DNA-binding properties are compared with those reported earlier for distamycin and NSC 101327 [Zimmer, Ch., & Wahnert, U. (1986) Prog. Biophys. Mol. Biol. 47, 31-1121. The backbone structures of these three ligands were compared to show the progressive decrease in curvatures in the order distamycin, mPD derivative, and NSC 101327. The plausible significance of the backbone curvature vis-&vis the characteristic B-DNA and AT-specific binding of distamycin is discussed. To our knowledge, this is the first attempt (with a model synthetic analogue) to probe the possible influence of backbone curvature upon the specificity of interactions of the distamycin class of groove-binding ligands with DNA.

Interannual Variations of Sea Surface Temperature over the Arabian Sea and the Indian Monsoon: A New Perspective

The interannual variation of surface fields over the Arabian Sea and Bay of Bengal are studied using data between 1900 and 1979. It is emphasized that the monthly mean sea surface temperature (SST) over the north Indian Ocean and monsoon rainfall are significantly affected by synoptic systems and other intraseasonal variations. To highlight the interannual signals it is important to remove the large-amplitude high-frequency noise and very low frequency long-term trends, if any. By suitable spatial and temporal averaging of the SST and the rainfall data and by removing the long-term trend from the SST data, we have been able to show that there exists a homogeneous region in the southeastern Arabian Sea over which the March�April (MA) SST anomalies are significantly correlated with the seasonal (June�September) rainfall over India. A potential of this premonsoon signal for predicting the seasonal rainfall over India is indicated. It is shown that the correlation between the SST and the seasonal monsoon rainfall goes through a change of sign from significantly positive with premonsoon SST to very small values with SST during the monsoon season and to significantly negative with SST during the post-monsoon months. For the first time, we have demonstrated that heavy or deficient rainfall years are associated with large-scale coherent changes in the SST (although perhaps of small amplitude) over the north Indian 0cean. We also indicate possible reasons for the apparent lack of persistence of the premonsoon SST anomalies.

Magnetic susceptibility studies on ternary oxides of copper(II)

The magnetic susceptibilities of a large number of ternary oxides of copper having structural features common to the presently identified phases of high-temperature superconductors have been studied in the temperature range 14-300 K. The systems studied are Ln2CuOP( Ln = La, Pr, Nd, etc.), Sr2CuO2CI2,B i2Cu0,, Ca2Cu03,S r2Cu03,S rCu02, MgCu203,B a2Cu3O4CI2Y, 2Cu205,Y2BaCu0,, BaCu02, Li2Cu02, etc. Cu2+ ions take different coordinations, like isolated square planar, square pyramidal or distorted-tetrahedral and octahedral, in these compounds. These compounds also exhibit different varieties of possible magnetic superexchange interactions like 180' or 90' Cu-0-Cu or Cu-0-0-Cu types as well as direct Cu-Cu interactions. Compounds in which there are extended 180' Cu-0-Cu interactions show a low, nearly temperature-independent susceptibility (100 X lod emu/mol). The estimated value of J for the Cu-0-Cu interaction is between 800 and 1500 K in these compounds. Isolated Cu2+ ions in which there are no 180' or close to 180" Cu-0-Cu interactions show Curie-Weiss susceptibility behavior. Compounds with only Cu-0-0-Cu interaction show evidence for the onset of antiferromagnetic coupling between 30 and 50 K. The superexchange rules are useful for explaining the qualitative features of the results. The possibility of disproportionation of Cu2+ ion when there are short Cu-Cu distances as in Bi2Cu04 is discussed. The extended geometry of the copper-oxygen framework seems to be more important than the local geometry around the Cu2+ ion in determining the magnetic properties.

Photochemical, photophysical, and theoretical studies on cyclobutanethiones..alpha.-Cleavage reactions

Photophysics and photochemistry of cyclobutanethiones 1-5 have been studied with the view to generalize the a-cleavage reactions of cyclobutanethiones. The above cyclobutanethiones possess a unit intersystem crossing efficiency from S1 to T1, a high self-quenching rate (-4 X lo9 M-' s-'), and a short triplet lifetime (<0.50 ws). Photolysis of 1-5 yields in benzene a product resulting from 1,3-transposition and in methanol two cyclic thioacetals.The origin of these products is traced to the triplet excited state. A mechanistic scheme involving a-cleavage as the primary photoprocess and diradicals and thiacarbenes as intermediates has been formulated to rationalize the formation of thioacetals and rearranged products. The proposed mechanistic scheme is supported by UHF MIND013 calculations performed on four model systems, cyclobutanethiones and 1,3-cyclobutanedithiones 18-21. These calculations indicate that formation of diradical is favored thermodynamically and kinetically for systems analogous to 19 and 21, while rearrangement to thiacarbene is likely only for those similar to 21.

Photochemistry of .alpha.,.beta.-unsaturated thiones: addition to electron-rich olefins from T1

1,1,3-Trimethyl-2-thioxo-1,2-dihydronaphthale(1n)e adds to electron-rich olefins upon excitation to either Sz (PP*) or Sl (ns*) states. Excitation to S2 level resulted in the same mixture of products, namely thietane and 1,4-dithiane, as on excitation to S1 level. Addition occurs to the thiocarbonyl function and not to the carbon-carbon double bond. The addition is site-specific, and the formation of thietane is regiospecific. The ratio of thietane to 1,4-dithiane in the product mixture is dependent on the concentration of the thioenone. The addition is suggested to originate from the lowest triplet state (Tl) and involves diradical intermediates.

Photochemistry of .alpha.,.beta.-unsaturated thiones. Cycloaddition to electron-deficient olefins from higher excited states

Electron-deficient olefins add to thioenone 1 upon m* excitation. Cycloaddition occurs to the thiocarbonyl chromophore preferentially from the less-hindered side to yield thietanes. Thietane formation is stereospecific and regioselective. This addition has been inferred to originate from the second excited singlet, S2(?rx*), state. The exciplex intermediacy has been inferred from the dependence of the fluorescence quenching rate constant on the electron-acceptor properties of the olefin. The observed site specificity and regioselectivity are rationalized on the basis of PMO theory. The observed photochemical behavior of thioenone is different from that of enones.

Parametrized tests of post-Newtonian theory using Advanced LIGO and Einstein Telescope

General relativity has very specific predictions for the gravitational waveforms from inspiralling compact binaries obtained using the post-Newtonian (PN) approximation. We investigate the extent to which the measurement of the PN coefficients, possible with the second generation gravitational-wave detectors such as the Advanced Laser Interferometer Gravitational-Wave Observatory (LIGO) and the third generation gravitational-wave detectors such as the Einstein Telescope (ET), could be used to test post-Newtonian theory and to put bounds on a subclass of parametrized-post-Einstein theories which differ from general relativity in a parametrized sense. We demonstrate this possibility by employing the best inspiralling waveform model for nonspinning compact binaries which is 3.5PN accurate in phase and 3PN in amplitude. Within the class of theories considered, Advanced LIGO can test the theory at 1.5PN and thus the leading tail term. Future observations of stellar mass black hole binaries by ET can test the consistency between the various PN coefficients in the gravitational-wave phasing over the mass range of 11-44M(circle dot). The choice of the lower frequency cutoff is important for testing post-Newtonian theory using the ET. The bias in the test arising from the assumption of nonspinning binaries is indicated.

Mixed Azide and 5-(Pyrimidyl)tetrazole Bridged Co(II)/Mn(II) Polymers: Synthesis, Crystal Structures, Ferroelectric and Magnetic Behavior

The reaction of pyrimidine-2-carbonitrile, NaN3 in the presence of Co(NO3)(2)center dot 6H(2)O or MnCl2 center dot 4H(2)O leads to the formation of complexes Co(pmtz)(mu(1,3)-N-3)(H2O)](n) (1) and Mn(pmtz)(mu(1,3)-N-3)(H2O)](n) (2) respectively, under hydrothermal condition pmtz =5-(pyrimidyl)tetrazolate]. These two complexes have been fully characterized by single crystal X-ray diffraction. Complex 1 crystallizes in a non-centrosymmetric space group Aba2 in the orthorhombic system and is found to exhibit ferroelectric behavior, whereas complex 2 crystallizes in the P2(1)/c space group in the monoclinic system. Variable temperature magnetic characterizations in the temperature range of 2-300 K indicate that complex 1 is a canted antiferromagnet (weak ferromagnet) with T-c = 15.9 K. Complex 1 represents a unique example of a multiferroic coordination polymer containing tetrazole as a co-ligand. Complex 2 is a one-dimensional chain of Mn(II) bridged by a well-known antiferromagnetic coupler end-to-end azido ligand. In contrast to the role played by the end-to-end azido pathway in most of the transition metal complexes, complex 2 showed unusual ferromagnetic behavior below 40 K because of spin canting.

Rearrangement of homobrendane derivatives. Total syntheses of racemic copacamphor, ylangocamphor, and their homologs

Rearrangement of a homobrendane derivative 8a to perhydro-1,4-methanoindenesy stem 9a could be brought about either by p-toluenesulfonic acid or boron trifluoride etherate. Similarly, rearrangement of 8b-d led to the formation of perhydro-1,4-methanoindened erivatives 9b-d. On the basis of the location of substituents in the starting material and the product, a probable mechanistic pathway has been suggested. The appropriate modification of the peripheral functionalities in 9 led to efficient total syntheses of (f)-copacamphor (15a),(f)-ylangocamphor (16a), and their homologues 15b and 16b.