Combustion synthesis of rare earth cuprates

Rare earth cuprates, La2CuO4 Nd2CuO4, La1.8M0.2CuO4 (M=Ca.Sr) and Nd1.85Ce0.15CuO4 have been prepared by the combustion of redox mixtures containing corresponding metal nitrates and maleic hydrazide, C4H4N2O2, at 350°C. The solid combustion products are submicron size amorphous powders which on heat treatment (700°C, 30 minutes) yield crystalline single phase cuprates. Strontium doped lanthanum cuprate, La1.8Sr0.2CuO4, shows an onset of superconductivity at 36K.

Combustion Synthesis and Properties of Fine Particle Spinel Manganites

Fine particle spinel manganites have been prepared by thermal decomposition of the precursors N2H5M1/3Mn2/3(N2H3COO)3 · H2O (M = Co and Ni) and M1/3 Mn2/3(N2H3COO)2 · 2H2O (M = Mg and Zn), as well as by the combustion of redox mixtures containing M(II) nitrate (M = Mg, Co, Ni, Cu, and Zn), Mn(II) nitrate, and maleic hydrazide (MH) in the required molar ratio. Both the precursor and redox mixtures undergo self-propagating, gas-producing, exothermic reactions once ignited at 250-375°C to yield corresponding manganites in less than 5 min. Formation of single phase products was confirmed by X-ray powder diffraction patterns. The manganites are of submicrometer size and have surface area in the range 20-76 m2/g.

Molecular structure of electron donor-acceptor complexes of metallotetraphenylporphyrins with trinitrobenzene

The metallotetraphenylporphyrins, MTPPs, where M=Co(II), Cu(II) and Ag(II) form one to one molecular complexes in solution with 1,3,5-trinitrobenzene (TNB). The crystal structure of CoTPP.TNB.2CH3OH revealed that the mean separation between the porphyrin and TNB planes is 3·27 Å and the centre of the aryl ring of TNB is displaced by 0·90 Å from the centre of the porphyrin plane. Extended Huckel molecular orbital calculations suggest that acceptor orbitals are predominantly nitro-group based rather than an aryl π framework. The contribution of the metal orbitals in the donation is also seen as predicted by the structural data. Electrochemical redox measurements in solution provide evidence for charge-transfer stabilisation in these complexes.

Sensitivity of wetland methane emissions to model assumptions: application and model testing against site observations

Abstract. Methane emissions from natural wetlands and rice paddies constitute a large proportion of atmospheric methane, but the magnitude and year-to-year variation of these methane sources is still unpredictable. Here we describe and evaluate the integration of a methane biogeochemical model (CLM4Me; Riley et al., 2011) into the Community Land Model 4.0 (CLM4CN) in order to better explain spatial and temporal variations in methane emissions. We test new functions for soil pH and redox potential that impact microbial methane production in soils. We also constrain aerenchyma in plants in always-inundated areas in order to better represent wetland vegetation. Satellite inundated fraction is explicitly prescribed in the model because there are large differences between simulated fractional inundation and satellite observations. A rice paddy module is also incorporated into the model, where the fraction of land used for rice production is explicitly prescribed. The model is evaluated at the site level with vegetation cover and water table prescribed from measurements. Explicit site level evaluations of simulated methane emissions are quite different than evaluating the grid cell averaged emissions against available measurements. Using a baseline set of parameter values, our model-estimated average global wetland emissions for the period 1993–2004 were 256 Tg CH4 yr−1, and rice paddy emissions in the year 2000 were 42 Tg CH4 yr−1. Tropical wetlands contributed 201 Tg CH4 yr−1, or 78 % of the global wetland flux. Northern latitude (>50 N) systems contributed 12 Tg CH4 yr−1. We expect this latter number may be an underestimate due to the low high-latitude inundated area captured by satellites and unrealistically low high-latitude productivity and soil carbon predicted by CLM4. Sensitivity analysis showed a large range (150–346 Tg CH4 yr−1) in predicted global methane emissions. The large range was sensitive to: (1) the amount of methane transported through aerenchyma, (2) soil pH (± 100 Tg CH4 yr−1), and (3) redox inhibition (± 45 Tg CH4 yr−1).

Organometallic chemistry of diphosphazanes. Part 7. Platinum(II), palladium-(o), -(I) and -(II) complexes of RN[P(OPh)2]2(R = Me or Ph)

The reactions of [MCl2(cod)](M = Pd or Pt, cod = cycloocta-1,5-diene) with RN[P(OPh)2]2[R = Me (L1) or Ph (L2)] afford the chelate complexes [MCl2L1] and [MCl2L2]. The dinuclear palladium(O) complex, [Pd2L13] has been synthesized by starting from [Pd2(dba)3](dba = dibenzylideneacetone). Redox condensation of [Pd2(dba)3] and [PdCl2(PhCN)2] in the presence of the diphosphazane ligands gives the dinuclear palladium(I) complexes [Pd2Cl2L12] and [Pd2Cl2L22]. The structures of the complexes have been deduced from 1H and 31P NMR spectroscopic data. Single-crystal X-ray diffraction studies confirm the structures of [Pd2L13] and [Pd2Cl2L22].

Conformational analysis and design of cross-strand disulfides in antiparallel beta-sheets

Cross-strand disulfides bridge two cysteines in a registered pair of antiparallel beta-strands. A nonredundant data set comprising 5025 polypeptides containing 2311 disulfides was used to study cross-strand disulfides. Seventy-six cross-strand disulfides were found of which 75 and 1 occurred at non-hydrogen-bonded (NHB) and hydrogen-bonded (HB) registered pairs, respectively. Conformational analysis and modeling studies demonstrated that disulfide formation at HB pairs necessarily requires an extremely rare and positive chi(1) value for at least one of the cysteine residues. Disulfides at HB positions also have more unfavorable steric repulsion with the main chain. Thirteen pairs of disulfides were introduced in NHB and HB pairs in four model proteins: leucine binding protein (LBP), leucine, isoleucine, valine binding protein (LIVBP), maltose binding protein (MBP), and Top7. All mutants LIVBP T247C V331C showed disulfide formation either on purification, or on treatment with oxidants. Protein stability in both oxidized and reduced states of all mutants was measured. Relative to wild type, LBP and MBP mutants were destabilized with respect to chemical denaturation, although the sole exposed NHB LBP mutant showed an increase of 3.1 degrees C in T-m. All Top7 mutants were characterized for stability through guanidinium thiocyanate chemical denaturation. Both exposed and two of the three buried NHB mutants were appreciably stabilized. All four HB Top7 mutants were destabilized (Delta Delta G(0) = -3.3 to -6.7 kcal/mol). The data demonstrate that introduction of cross-strand disulfides at exposed NHB pairs is a robust method of improving protein stability. All four exposed Top7 disulfide mutants showed mild redox activity. Proteins 2011; 79: 244-260. (C) 2010 Wiley-Liss, Inc.

Cobalt(II) complexes of terpyridine bases as photochemotherapeutic agents showing cellular uptake and photocytotoxicity in visible light

Cobalt(II) complexes of terpyridine bases Co(L)(2)](ClO4)(2) (1-3), where L is 4'-phenyl-2,2':6',2''-terpyridine (ph-tpy in 1), 4'-(9-anthracenyl)-2,2':6',2''-terpyridine (an-tpy in 2) and 4'-(1-pyrenyl)-2,2':6',2''-terpyridine (py-tpy in 3), are prepared and their photo-induced DNA and protein cleavage activity and photocytotoxic property in HeLa cells studied. The 1 : 2 electrolytic and three-electron paramagnetic complexes show a visible band near 550 nm in DMF-Tris-HCl buffer. The complexes 1-3 show emission spectral bands at 355, 421 and 454 nm, respectively, when excited at 287, 368 and 335 nm. The quantum yield values for 1-3 in DMF-H2O (2 : 1 v/v) are 0.025, 0.060 and 0.28, respectively. The complexes are redox active in DMF-0.1 M TBAP. The Co(III)-Co(II) and Co(II)-Co(I) couples appear as quasi-reversible cyclic voltammetric responses near 0.2 and -0.7 V vs. SCE, respectively. Complexes 2 and 3 are avid binders to calf thymus DNA giving K-b value of similar to 10(6) M-1. The complexes show chemical nuclease activity. Complexes 2 and 3 exhibit oxidative cleavage of pUC19 DNA in UV-A and visible light. The DNA photocleavage reaction of 3 at 365 nm shows formation of singlet oxygen and hydroxyl radical species, while only hydroxyl radical formation is evidenced in visible light. Complexes 2 and 3 show non-specific photo-induced bovine serum albumin protein cleavage activity at 365 nm. The an-tpy and py-tpy complexes exhibit significant photocytotoxicity in HeLa cervical cancer cells on exposure to visible light giving IC50 values of 24.2 and 7.6 mu M, respectively. Live cell imaging study shows accumulation of the complexes in the cytosol of HeLa cancer cells.

Synthesis of A1PO4, LaPO4 and KTiOPO4 by flash combustion

Fine particle AlPO4, LaPO4 and KTiOPO4 have been prepared by the flash combustion of aqueous solutions containing metal nitrate, ammonium hydrogen phosphate, ammonium nitrate or ammonium perchlorate and carbohydrazide or tetraformal trisazine. When rapidly heated at 400 °C, the solution containing the redox mixtures ignites to undergo self-propagating, gas-producing, exothermic reactions. Formation of crystalline phosphates was confirmed by powder X-ray diffraction patterns and IR spectra. The metal phosphates formed are fine and have 20�78 m2 g?1 surface area.

Functions Of Cytochrome-C In Regulation Of Electron-Transfer And Protein Folding

Cytochrome c, a "mobile electron carrier" of the mitochondrial respiratory chain, also occurs in detectable amounts in the cytosol, and can receive electrons from cytochromes present in endoplasmic reticulum and plasma membranes as well as from superoxide and ascorbate. The pigment was found to dissociate from mitochondrial membranes in liver and kidney when rats were subjected to heat exposure and starvation, respectively. Treating cytochrome c with hydroxylamine gives a partially deaminated product with altered redox properties; decreased stimulation of respiration by deficient mitochondria, increased reduction by superoxide, and complete loss of reducibility by plasma membranes. Mitochondria isolated from brown adipose tissue of cold-exposed rats are found to be sub-saturated with cytochrome c. The ability of cytochrome c to reactivate reduced ribonuclease is now reinterpreted as a molecular chaperone role for the hemoprotein.

The Zintl ion As-7](2-): an example of an electron-deficient As-x radical anion

K(2,2,2-crypt)](2)As-7]center dot THF, 1 (2,2,2-crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo8.8.8]hexacosane) is the first well characterized seven-atom radical anion of group 15. UV-Vis spectroscopy confirms the presence and electronic structure of As-7](2-). Cyclic voltammetry in DMF solution shows the As-7(3) /As-7(2) redox couple as a one-electron reversible process. Theoretical investigations explore the bonding and properties of compound 1.

Combustion synthesis and properties of Ln3Fe5O12 and yttrium aluminium garnets

The rare earth iron garnets Ln3Fe5O12 and Y3AlxFe5-xO12, where x=1.0-5.0, and Y1.5Gd1.5Al0.2Fe4.8O12 have been prepared by the combustion of redox mixtures containing corresponding metal nitrates and oxalyl dihydrazide, i.e. C2H6N4O2 at 350-degrees-C. The solid combustion products are amorphous, submicrometre-sized powders which, on heating at 750-degrees-C for 3 h, yield crystalline single-phase garnets. The particle size of the garnets is below 1 mum and the surface area ranges from 16 to 90 m2 g-1. Yttrium iron garnet could be sintered to a density of more than 95% at 1200-degrees-C for 3 h, giving an average grain size of 3-5 mum.

DNA Photocleavage and Cytotoxic Properties of Ferrocene Conjugates

Ferrocenyl conjugates 2-ferrocenylimidazophenanthroline (1) and 2-ferrocenylimidazophenanthrene (2) were prepared, characterized, and their photoinduced DNA cleavage and photocytotoxic activity were studied. 2-Phenylimidazophenanthroline (3) was used as a control species. Compound 2 was characterized by X-ray crystallography. The interaction of the compounds with double-stranded calf thymus DNA (CT DNA) was studied. The compounds show good binding affinity to CT DNA with K-b values of approximately 10(5) M-1. Thermal denaturation data suggest the groove binding nature of the compounds. The redox-active compounds show poor chemical nuclease activity in the presence of hydrogen peroxide and glutathione (GSH). Compound 1 exhibits significant DNA photocleavage activity in visible light of 476 and 532 nm. Compound 3 shows only moderate DNA cleavage activity. The positive effect of the ferrocenyl moiety is demonstrated by the DNA photocleavage data. Mechanistic investigations reveal the formation of superoxide as well as hydroxyl radicals as the active species. The photocytotoxicity of the compounds in HeLa cells was studied upon irradiation with visible light (400-700 nm). Compound 1 shows efficient photocytotoxic activity with an IC50 value of 13 mu M, while compounds 2 and 3 are less active with IC50 values of > 50 and 22 mu M, respectively.

Terpyridine Oxovanadium(IV) Complexes of Phenanthroline Bases for Cellular Imaging and Photocytotoxicity in HeLa Cells

Oxovanadium(IV) complexes VO(N-N-N)(N-N)](NO3)(2) (1-4) of (4'-phenyl)-2,2': 6',2 `'-terpyridine (ph-tpy in 1 and 2) or (4'-pyrenyl)-2,2':6',2 `'-terpyridine (py-tpy in 3 and 4) having N-N as 1,10-phenanthroline (phen in 1 and 3) or dipyrido3,2-a:2',3'-c]phenazine (dppz in 2 and 4) are prepared and characterized. The crystal structure of 1 has VO2+ group in VN5O coordination geometry. The terpyridine ligand coordinates in a meridional binding mode. The phen ligand displays a chelating mode of binding with an N-donor site trans to the vanadyl oxo group. The complexes show a d-d band in the range of 710-770 nm in aqueous DMF (4:1 v/v). The complexes exhibit an irreversible V-IV/V-III redox response near -1.0 V vs. SCE in aqueous DMF/0.1 M KCl. The complexes bind to CT DNA giving K-b values within 3.5 x 10(5) to 1.2 x 10(6) M-1. The complexes show poor chemical nuclease activity in dark. Complexes 2-4 show photonuclease activity in UV-A light of 365 nm forming O-1(2) and (OH)-O-center dot. Complex 4 shows DNA photocleavage activity at near-IR light of 785 nm forming (OH)-O-center dot radicals. Complexes 2 and 4 show significant photocytotoxicity in HeLa cancer cells. Uptake of the complexes in HeLa cells, studied by fluorescence imaging, show predominantly cytosolic localization inside the cells.

Structure-Activity Relationship of Photocytotoxic Iron(III) Complexes of Modified Dipyridophenazine Ligands

Iron(III) complexes FeL(B)] (1-5) of a tetradentate trianionic phenolate-based ligand (L) and modified dipyridophenazine bases (B), namely, dipyrido-6,7,8,9-tetrahydrophenazine (dpqC in 1), dipyrido3,2-a:2',3'-c]phenazine-2-carboxylic acid (dppzc in 2), dipyrido3,2-a:2',3'-c]phenazine-11-sulfonic acid (dppzs in 3), 7-aminodipyrido3,2-a:2',3'-c]phenazine (dppza in 4) and benzoi]dipyridro3,2-a:2',3'-c]phenazine (dppn in 5), have been synthesized, and their photocytotoxic properties studied along with their dipyridophenazine analogue (6). The complexes have a five. electron paramagnetic iron(III) center, and the Fe(III)/Fe(II) redox couple appears at about 0.69 V versus SCE in DMF-0.1 M TBAP. The physicochemical data also suggest that the complexes possess similar structural features as that of its parent complex FeL(dppz)] with FeO3N3 coordination in a distorted octahedral geometry. The DNA-complex and protein-complex interaction studies have revealed that the complexes interact favorably with the biomolecules, the degree of which depends on the nature of the substituents present on the dipyridophenazine ring. Photocleavage Of pUC19 DNA by the complexes has been studied using visible light of 476, 530, and 647 nm wavelengths. Mechanistic investigations with inhibitors show formation of HO center dot radicals via a photoredox pathway. Photocytotoxicity study of the complexes in HeLa cells has shown that the dppn complex (5) is highly active in causing cell death in visible light with sub micromolar IC50 value. The effect of substitutions and the planarity of the phenazine moiety on the cellular uptake are quantified by determining the total Cellular iron content using the inductively coupled plasma-optical emission spectrometry (ICP-OES) technique. The cellular uptake increases marginally with an increase in the hydrophobicity of the dipyridophenazine ligands whereas complex 3 with dppzs shows very high uptake. Insights into the cell death mechanism by the dppn complex 5, obtained through DAFT nuclear staining in HeLa cells, reveal a rapid programmed cell death mechanism following photoactivation of complex 5 with visible light. The effect of substituent on the DNA photocleavage activity of the complexes has been rationalized from the theoretical studies.

Soft-chemical routes to synthesis of solid oxide materials

We describe three different families of metal oxides, viz., (i) protonated layered perovskites, (ii) framework phosphates of NASICON and KTiOPO4 (KTP) structures and (iii) layered and three-dimensional oxides in the H-V-W-O system, synthesized by 'soft-chemical' routes involving respectively ion-exchange, redox deinteracalation and acid-leaching from appropriate parent oxides. Oxides of the first family, HyA2B3O10(A = La/Ca; B = Ti/Nb), exhibit variable Bronsted acidity and intercalation behaviour that depend on the interlayer structure. V2(PO4)3 prepared by oxidative deintercalation from Na3V2(PO4)3 is a new host material exhibiting reductive insertion of lithium/hydrogen, while K0.5Nb0.5 M0.5OPO4(M = Ti, V) are novel KTP-like materials exhibiting second harmonic generation of 1064 nm radiation. HxVxW1-xO3 for x = 0.125 and 0.33 possessing alpha-MoO3 and hexagonal WO3 structures, prepared by acid-leaching of LiVWO6, represent functionalized oxide materials exhibiting redox and acid-base intercalation reactivity.