Catalytic hydrogen combustion for treatment of combustible gases from fuel cell processors

Catalytic combustion of H-2 was carried out over combustion synthesized noble metal (Pd or Pt) ion-substituted CeO2 based catalysts using a feed stream that simulated exhaust gases from a fuel cell processor The catalysts showed a high activity for H-2-combustion and complete conversion was achieved below 200 C over all the catalysts when O-2 was used in a stoichiometric amount With higher amounts of O-2 the reaction rates Increased and complete conversions were possible below 100 C The reaction was also carried out over Pd-impregnated CeO2 The conversions of H-2 with stoichiometric amount of O-2 were found to be higher over Pd-substituted compound The mechanism of the reaction over noble metal-substituted compounds was proposed on the basis of X-ray photoelectron spectroscopy studies The redox couples between Ce and metal ions were established and a dual site redox mechanism was pi posed for the reaction (C) 2010 Elsevier B V All rights reserved

Photo-activated cytotoxicity of a pyrenyl-terpyridine copper(II) complex in HeLa cells

Terpyridine copper(II) complexes Cu(L)(2)](NO3)(2) where L is (4'-phenyl)-2 2' 6' 2 `'-terpyridine (ph-tpy in 1) and 4-(1 pyrenyl)]-2 2' 6' 2'-terpyridine (py-tpy in 2) are prepared characterized and their photocytotoxic activity studied The crystal structure of complex 1 shows distorted octahedral CuN6 coordination geometry The 1 2 electrolytic and one-electron paramagnetic complexes show a visible band near 650 nm in DMF-H2O The complexes show emission band at 352 nm for 1 and 425 nm for 2 when excited at 283 and 346 nm respectively The Cu(II)-Cu(I) redox couple is observed near -0 2 V versus SCE in DMF-0 1 m TBAP The complexes are avid partial-intercalative binders to calf thymus DNA giving binding constant (K-b) values of similar to 10(6) M-1 Complex 2 with its photoactive pyrenyl moiety exhibits significant photocleavage of pUC19 DNA in red light via singlet oxygen pathway Complex 2 also exhibits significant photo-activated cytotoxicity in HeLa cancer cells in visible light giving IC50 value of 11 9 mu M while being non-toxic in dark with an IC50 value of 130 5 mu M (C) 2010 Elsevier Ltd All rights reserved

Phenyl-Ring-Bearing Cationic Surfactants: Effect of Ring Location on the Micellar Structure

A series of isomeric cationic surfactants (S1-S5) bearing a long alkyl chain that carries a 1,4-phenylene unit and a trimethyl ammonium headgroup was synthesized; the location of the phenyl ring within the alkyl tail was varied in an effort to understand its influence on the amphiphilic properties of the surfactants. The cmc's of the surfactants were estimated using ionic conductivity measurements and isothermal calorimetric titrations (ITC); the values obtained by the two methods were found to be in excellent agreement. The ITC measurements provided additional insight into the various thermodynamic parameters associated with the micellization process. Although all five surfactants have exactly the same molecular formula, their micellar properties were seen to vary dramatically depending on the location of the phenyl ring; the cmc was seen to decrease by almost an order of magnitude when the phenyl ring was moved from the tail end (cmc of S1 is 23 mM) to the headgroup region (cmc of S5 is 3 mM). In all cases, the enthalpy of micellization was negative but the entropy of micellization was positive, suggesting that in all of these systems the formation of micelles is both enthalpically and entropically favored. As expected, the decrease in cmc values upon moving the phenyl ring from the tail end to he headgroup region is accompanied by an increase in the thermodynamic driving force (Delta G) for micellization. To understand further the differences in the micellar structure of these surfactants, small-angle neutron scattering (SANS) measurements were carried out; these measurements reveal that the aggregation number of the micelles increases as the cmc decreases. This increase in the aggregation number is also accompanied by an increase in the asphericity of the micellar aggregate and a decrease in the fractional charge. Geometric packing arguments are presented to account for these changes in aggregation behavior as a function of phenyl ring location.

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.

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.