Transformation of mixed anionic coordination polymers of lead

The coordination polymerization from lead(II) nitrate on reaction with 4-nitrobenzoic acid and pyridine N-oxide at room temperature passes through stepwise ligand substitution reaction. An intermediate polymer [Pb(NB)(PyO)₂(NO₃)]_n (where NB = 4-nitrobenzoate, PyO = Pyridine N-oxide) is formed to give the final polymer [Pb(NB)₂(PyO)]_n. A hydrated mononuclear complex [Pb(NB)₂(PyO)(H₂O)] is also formed if rigorous anhydrous condition is not maintained. The reaction is extended to 4,4′-bipyridyl N-oxide (BPNO), which initially gives a coordination polymer [Pb₂(NO₃)(NB)₃(BPNO)₂]_n which gets converted to another coordination polymer [Pb(NB)₂(BPNO)₂]_n. All these complexes are structurally characterized.     

Synthesis and characterization of pyridine N-oxide complexes of manganese, copper and zinc

A series of metal carboxylates containing pyridine N-oxide are prepared via one pot synthesis and solid phase synthesis. The structural variations from metal to metal are observed. In the case of reactions of manganese(II) acetate with pyridine N-oxide in the presence of aromatic carboxylic acids, polymeric complexes with bridging aromatic carboxylate as well as bridging pyridine N-oxide are observed. Whereas, the reaction of copper(II) acetate with pyridine N-oxide in the presence of an aromatic carboxylic acid led to mononuclear or binuclear paddle wheel carboxylate complexes with monodentate pyridine N-oxide. Co-crystal of two neutral complexes having composition [Cu₂(OBz)₄(MeOH)₂][Cu₂(OBz)₄(pyO)₂] (where OBz = benzoate, pyO = pyridine N-oxide) each neutral parts have paddle wheel structure. Solid phase reaction of zinc chloride with sodium benzoate prepared in situ and pyridine N-oxide leads to a tetra-nuclear zinc complex.     

Stability and motion of a hairpin and the corresponding mismatched duplex: a theoretical exploration using molecular mechanics and normal mode analysis of 2D NMR results on d(GCCGCAGC)

The oligomer d(GCCGCAGC) can adopt two different conformations: i) a duplex with two mismatched A.C base pairs and ii) a hairpin with two C.G base pairs and a single stranded loop. We report molecular mechanics, normal mode analysis, and thermodynamic stability calculations for both structures. We show that the energy-minimized structure and harmonic-dynamics results are in complete agreement with the observed NOE spectrum and imino proton exchange data. We conclude that the high stability of the hairpin structure over the duplex at low salt concentration is due to the higher vibrational entropy contribution to the system free energy by the single stranded loop and to the lack of minor groove phosphate/phosphate electrostatic repulsions that tend to destabilize the duplex.     

Conformational microheterogeneity in a DNA double helix: structure of restriction endonuclease Bam H1 recognition site

Structural studies using 500 MHz 1H NMR spectroscopy on Bam H1 recognition site d(GGATCC)2 in solution at 19 degrees is reported. The resonances from the sugar ring and base protons have been assigned from the 2D-COSY and NOESY spectra. Analyses of the NOESY cross-peaks between the base protons H8/H6 and sugar protons H2'/H2", H3' reveal that the nucleotide units G2, A3 and C6 adopt (C3'-endo, chi = 200 degrees-220 degrees) conformation while G1, T4 and C5 exhibit (C2'-endo, chi = 240 degrees-260 degrees) conformation. NMR data clearly suggest that the two strands of d(GGATCC)2 are conformationally equivalent and there is a structural two-fold between the two A-T pairs. The above information and the NOESY data are used to generate a structural model of d(GGATCC)2. The important features are: (i) G1-G2 stack, the site of cleavage, shows an alternation in sugar pucker i.e. C2'-endo, C3'-endo as in a B-A junction, (ii) G2-A3 stack adopts a mini A-DNA, both the sugars being C3'-endo, (iii) A3-T4 stack, the site of two-fold, displays an A-B junction with alternation in sugar pucker as C3'-endo, C2'-endo, (iv) T4-C5 stack adopts a mini B-DNA both the sugars being C2'-endo and (v) C5-C6 stack exhibits a B-A junction with C2'-endo, C3'-endo sugar puckers. Thus, our studies demonstrate that conformational microheterogeneity with a structural two fold, is present in the Bam H1 recognition site.     

MECHANISM OF ACTION OF β-N-OXALYL-L-α, β-DIAMINOPROPIONIC ACID, THE LATHYRUS SATIVUS NEUROTOXIN

The source of ammonia in the brain tissue of young rats treated with β-N-oxalyl-l -α, β-diaminopropionic acid (ODAP) has been studied. ODAP administration to 12-day-old rats causes a significant increase in the levels of adenylic acid deaminase in the brain. Glutaminase activity also shows an increase under these conditions. An increase in the levels of acid protease and transglutaminase is also observed in the brain of ODAP-treated animals. Glutamate dehydrogenase activity is decreased slightly. Glutamine synthetase enzyme is not affected. Aspartate-α-ketoglutarate transaminase and aspartate-pyruvate transaminase activities are enhanced in the brain tissue of ODAP-treated rats. It is held that protein degradation, especially the cleavage of free and protein-bound amide bonds, may be responsible for excess ammonia liberation in the brain of ODAP-treated young rats.