Synthesis, reactivity and structural characterisation of bicyclic tetraphosphapentazanes

The diphenoxy bicyclic tetraphosphapentazane derivatives (EtN)(5)P-4(OPh)(2) 2 and its monoxide (EtN)(5)P-4(O)(OPh)(2) 3 have been prepared. Both 2 and 3 exist as a mixture of two isomers. One isomer of (EtN)(5)P-4(O)(OPh)(2) 3a has been isolated and its reaction with tetrachloro-1,2-benzoquinone yielded (EtN)(5)P-4(O)(OPh)(2)(O2C6Cl4) 5 in which the junction phosphorus atom becomes five-co-ordinated. Treatment of 2 or 3a with [Mo(CO)(4)(nbd)] (nbd = norbornadiene, bicyclo[2.2.1]hepta-2,5-diene), on the other hand, yielded the chelate complex [Mo(CO)(4){(EtN)(5)P-4(O)(n)(OPh)(2)}] (n = 0 or 1; 6 or 7) in which the peripheral phosphorus atoms are bonded to the metal. The structures of 3a and 5-7 have been confirmed by single-crystal X-ray diffraction studies. The two P3N3 rings in 3a and 5 adopt twist/twist and irregular/twist conformations respectively; the phenoxy substituents occupy the 'pseudo axial' positions. However, an ideal chair conformation is observed for the P3N3 rings in 6 and 7 with the phenoxy substituents taking up the 'pseudo equatorial' positions. The NMR spectroscopic data for the compounds are discussed.

Localisation of Plasmodium falciparum uroporphyrinogen III decarboxylase of the heme-biosynthetic pathway in the apicoplast and characterisation of its catalytic properties

Uroporphyrinogen decarboxylase (UROD) is a key enzyme in the heme-biosynthetic pathway and in Plasmodium falciparum it occupies a strategic position in the proposed hybrid pathway for heme biosynthesis involving shuttling of intermediates between different subcellular compartments in the parasite. In the present study, we demonstrate that an N-terminally truncated recombinant P. falciparum UROD (r(Δ)PfUROD) over-expressed and purified from Escherichia coli cells, as well as the native enzyme from the parasite were catalytically less efficient compared with the host enzyme, although they were similar in other enzyme parameters. Molecular modeling of PfUROD based on the known crystal structure of the human enzyme indicated that the protein manifests a distorted triose phosphate isomerase (TIM) barrel fold which is conserved in all the known structures of UROD. The parasite enzyme shares all the conserved or invariant amino acid residues at the active and substrate binding sites, but is rich in lysine residues compared with the host enzyme. Mutation of specific lysine residues corresponding to residues at the dimer interface in human UROD enhanced the catalytic efficiency of the enzyme and dimer stability indicating that the lysine rich nature and weak dimer interface of the wild-type PfUROD could be responsible for its low catalytic efficiency. PfUROD was localised to the apicoplast, indicating the requirement of additional mechanisms for transport of the product coproporphyrinogen to other subcellular sites for its further conversion and ultimate heme formation.

Synthesis and characterisation of heterometallic molecular triangles using ambidentate linker: self-selection of a single linkage isomer

The coordination driven self-assembly of discrete molecular triangles from a non-symmetric ambidentate linker 5-pyrimidinecarboxylate (5-pmc) and Pd(II)/Pt(II) based 90◦ acceptors is presented. Despite the possibility of formation of a mixture of isomeric macrocycles (linkage isomers) due to different connectivity of the ambidentate linker, formation of a single and symmetrical linkage somer in both the cases is an interesting observation. Moreover, the reported macrocycles represent the first example of discrete metallamacrocycles of bridging 5-pmc. While solution composition in both the cases was characterised by multinuclear NMR study and electrospray ionization mass spectrometry (ESI-MS), the identity of the assemblies in the solid state was established by X-ray single crystals structure analysis. Variable temperature NMR study clearly ruled out the formation of any other macrocycles by [4 + 4] or [2 + 2] self-assembly of the reacting components.

Characterisation of k-Variegated Graphs, k greater-than-or-equal-to 3

A graph is said to be k-variegated if its vertex set can be partitioned into k equal parts such that each vertex is adjacent to exactly one vertex from every other part not containing it. Bednarek and Sanders [1] posed the problem of characterizing k-variegated graphs. V.N. Bhat-Nayak, S.A. Choudum and R.N. Naik [2] gave the characterization of 2-variegated graphs. In this paper we characterize k-variegated graphs for k greater-or-equal, slanted 3.

Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes

Metal hydrazine nitrate complexes of the type M(N2H4)Nn (NO3)2 where M = Mg, n = 2; M = Mn, Fe, Co, Ni, Zn and Cd and n = 3; metal dihydrazine azide complexes of the type M(N2H4)2 (N3)2 where M = Mg, Co, Ni and Zn; and Mg(N2H4)2 (C1O4)2 have been prepared by dissolving the respective metal powders in the solution of corresponding ammonium salts (NO3, N3 and C1O4) in hydrazine hydrate. These hydrazine complexes were also prepared by the conventional method involving the addition of alcoholic hydrazine hydrate to the aqueous solution of metal salts. The hydrazine complexes have been characterised by chemical analysis, infrared spectra and differential thermal analysis (DTA). Impact sensitivities of hydrazine complexes were determined by the drop weight method. The reactivity of these hydrazine complexes does not change with the method of preparation.

X-ray and IR characterisation of Nasicon solid solution, Na1+xZr2SixP3−xO12

X-ray and IR studies on Nasicon solid solutions, Na1+xZr2SixP3−xO12, are carried out as a function of composition x. X-ray diffraction studies show that the unit cell volume increases as x increases and exhibits a maximum at x ≈ 2. On further increase in x the unit cell volume decreases. The infrared absorption peak positions and the splitting of these absorption peaks suggest a distortion of the PO4 and SiO4 tetrahedra. But the distortion is not large enough to change the local symmetry around the phosphorus or silicon ion from Td to C3v.

Preparation, characterisation and thermal properties of hydrazinium derivatives. Part III

Hydrazinium acetate, metavanadate, sulfite, sulphamate and thiocyanate have been prepared by the reaction of corresponding ammonium salts with hydrazine hydrate. The compounds were characterised by chemical analysis and infrared spectra. Thermal behaviour of these hydrazinium derivatives have been investigated using thermogravimetry and differential thermal analysis.

Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes

Metal hydrazine nitrate complexes of the type M(N2H4)Nn (NO3)2 where M = Mg, n = 2; M = Mn, Fe, Co, Ni, Zn and Cd and n = 3; metal dihydrazine azide complexes of the type M(N2H4)2 (N3)2 where M = Mg, Co, Ni and Zn; and Mg(N2H4)2 (C1O4)2 have been prepared by dissolving the respective metal powders in the solution of corresponding ammonium salts (NO3, N3 and C1O4) in hydrazine hydrate. These hydrazine complexes were also prepared by the conventional method involving the addition of alcoholic hydrazine hydrate to the aqueous solution of metal salts. The hydrazine complexes have been characterised by chemical analysis, infrared spectra and differential thermal analysis (DTA). Impact sensitivities of hydrazine complexes were determined by the drop weight method. The reactivity of these hydrazine complexes does not change with the method of preparation.

Conformational characterisation of valinomycin complexation with barium salts:A nuclear magnetic resonance spectroscopic study

Conformations of valinomycin and its complexes with Perchlorate and thiocyanate salts of barium, in a medium polar solvent acetonitrile, were studied using nuclear magnetic resonance spectroscopic techniques. Valinomycin was shown to have a bracelet conformation in acetonitrile. With the doubly charged barium ion, the molecule, at lower concentrations, predominantly formed a 1:1 complex. At higher concentrations, however, apart from the 1:1, peptide as well as ion sandwich complexes were formed in addition to a :final complex:. Unlike the standard 1:1 potassium complex, where the ion was centrally located in a bracelet conformation, the a 1:1 barium complex contained the barium ion at the periphery. The a :final complex: appeared to be an open conformation with no internal hydrogen bonds and has two bound barium ions. This complex was probably made of average of many closely related conformations that were exchanging very fast (on nuclear magnetic resonance time scale) among them. The conformation of the a:final complex a: resembled the conformation obtained in the solid state. Unlike the Perchlorate anion, the thiocyanate anion seemed to have a definite role in stabilising the various complexes. While the conformation of the 1:1 complex indicated a mechanism of ion capture at the membrane interface, the sandwich complexes might explain the transport process by a relay mechanism.

Preparation, Characterisation and Thermal Properties of Hydrazinium Magnesium Sulfate

Hydrazinium magnesium sulfate, (N2H5)2Mg(SO4)2, has been prepared by dissolving magnesium powder in a solution of ammonium sulfate in hydrazine hydrate, by the reaction of ammonium magnesium sulfate with hydrazine hydrate, and by the cocrystallisation of dihydrazinium sulfate and magnesium sulfate. The product has been characterized by chemical analysis and infrared spectra. Thermal analysis of (N2H5)2Mg(SO4)2 by TG and DTA show exothermic decomposition at 302°C giving Mg(N2H4)SO4 as an intermediate and an endother-mic decomposition at 504°C producing MgSO4.

Characterisation of the DNA-polymerase-alpha-primase complex from the silk glands of Bombyx mori

Silk gland cells ofBombyx mori undergo chromosomal endoduplication throughout larval development. The DNA content of both posterior and middle silk gland nuclei increased by 300000 times the haploid genomic content, amounting to 18 rounds of replication. The DNA doubling time is approximately 48 h and 24 h during the fourth and fifth instars of larval development. However, DNA content does not change during the interim moult. Concomitant with DNA content, DNA polymerase activity also increases as development progressed. Enzyme activity is predominantly due to DNA polymerase with no detectable level of polymerase . DNA polymerase from silk gland extracts was purified to homogeneity (using a series of columns involving ionexchange, gel-filtration and affintiy chromatography), resulting in a 4000-fold increase in specific activity. The enzyme is a heterogeneous multimer of high molecular mass, and the catalytic (polymerase) activity is resident in the 180-kDa subunit. The enzyme shows a PI of 6.2 and theKm values for the dNTP vary over 5-16 . The polymerase is tightly associated with primase activity and initiates primer synthesis in the presence of ribonucleoside triphosphates on a single-stranded DNA template. The primase activity is resident in the 45-kDa subunit. The enzyme is devoid of any detectable exonuclease activity. The abundance of DNA polymerase α in silk glands and its strong association with the nuclear matrix suggest a role in the DNA endoduplication process.

Rice husk filtrate as a nutrient medium for the growth of Desulfotomaculum nigrificans: characterisation and sulfate reduction studies

The filtrate obtained by interacting a known amount of rice husk with deionised, Milli-Q water was assessed as a carbon source and nutrient medium for the growth of Desulfotomaculum nigrificans, a typical sulfate-reducing bacterium. The filtrate contained essential growth constituents such as magnesium, potassium, phosphorous apart from calcium, sodium, chloride and sulfate ions. Based on the 1H and 13C NMR characterization studies, the organic composition of the components dissolved from the rice husk, was found to be: (i) 66% lignocellulosic material, (ii) 24% xylose + arabinose and (iii) 10% galactose. The growth studies indicated a 15-fold increase in the bacterial cell number in about 20 days. Nearly 81% and 66% reduction in sulfate concentration could be achieved in about 28 days, from the solutions containing initial sulfate concentrations of 550 mg/l and 1200 mg/l respectively. In both the cases studied, the iron concentration could be reduced by over 85%.

Molecular characterisation of ABC transporter type FtsE and FtsX proteins of Mycobacterium tuberculosis.

Elicitation of drug resistance and various survival strategies inside host macrophages have been the hallmarks of Mycobacterium tuberculosis as a successful pathogen. ATP Binding Cassette (ABC) transporter type proteins are known to be involved in the efflux of drugs in bacterial and mammalian systems. FtsE, an ABC transporter type protein, in association with the integral membrane protein FtsX, is involved in the assembly of potassium ion transport proteins and probably of cell division proteins as well, both of which being relevant to tubercle bacillus. In this study, we cloned ftsE gene of M. tuberculosis, overexpressed and purified. The recombinant MtFtsE-6xHis protein and the native MtFtsE protein were found localized on the membrane of E. coli and M. tuberculosis cells, respectively. MtFtsE-6xHis protein showed ATP binding in vitro, for which the K42 residue in the Walker A motif was found essential. While MtFtsE-6xHis protein could partially complement growth defect of E. coli ftsE temperature-sensitive strain MFT1181, co-expression of MtFtsE and MtFtsX efficiently complemented the growth defect, indicating that the MtFtsE and MtFtsX proteins might be performing an associated function. MtFtsE and MtFtsX-6xHis proteins were found to exist as a complex on the membrane of E. coli cells co-expressing the two proteins.

Stabilisation and characterisation of N,N′-dibenzylidene-o-phenylenediamine as a copper(I) perchlorate complex

QUITE OFTEN, metal ions profoundly affect the condensation of carbonyl compounds with primary amines to form Schiff bases as well as their subsequent reactions[I-4]. Condensation of benzaldehyde with o-phenylenediamine (opd) in glacial acetic acid[5] or in absolute alcohol[6] gives benzimidazole derivative, 1-benzyl-2-phenylbenzimidazole (bpbi). In this reaction, the Schiff base N,N'-dibenzylidene-o-phenylenedianfme (dbpd) has been postulated as an intermediate, which cyclises to give bpbi. It was found that the reaction of opd in presence of copperO1) perchlorate with benzaldehyde gave dbpd complex of copper(l) perchlorate instead of bpbi.

Synthesis, characterisation and thermal analysis of copper (II) and chromium (II, III) hydrazine carboxylates

Copper(II) hydrazine carboxylate monohydrate, Cu(N2H3COO)2·H2O and chromium (II, III) hydrazine carboxylate hydrates, Cu(N2H3COO)2·H2O and Cu(N2H3COO)2·3H2O have been prepared and characterised by chemical analysis, IR, visible spectra and magnetic measurements. Thermal analysis of the copper complex yields a mixture of copper metal and copper oxide. Chromium complexes on thermal decomposition yield Cr2O3 as residue. Decomposition of chromium(HI) complex under hydrothermal conditions yield CrOOH, a precursor to CrO2.