Thermochromism and structure of piperazinium tetrachlorocuprate(II) complexes

The tetrachlorocuprate(II) ion can crystallize in two different structures with the piperazinium dication (pipzH(2)). Both structures contain discrete CuCl42- species. A yellow compound (pipzH(2))[CuCl4]. 2H(2)O (1) is monoclinic (C2/c, Z = 4, a = 10.538(3) Angstrom, b = 7.4312(5) Angstrom, c = 17.281(4) Angstrom, beta = 111.900(10)degrees) and contains the CuCl42- ion as a distorted tetrahedron. A green compound (pipzH(2))(2)[CuCl4]. Cl-2. 3H(2)O (2) is triclinic (P (1) over bar, Z = 2, a = 9.264(3) Angstrom, b = 10.447(2) Angstrom, c = 11.366(2) Angstrom, alpha = 68.38 degrees, beta = 82.86(2)degrees, gamma = 83.05(2)degrees) and contains the CuCl42- ion with a square planar geometry. This latter compound shows thermo/photochromism, changing from green to yellow upon heating or laser irradiation.

Preparation, characterization, and catalytic properties of clay-based nickel catalysts for methane reforming

Naturally occurring clays and pillared clays are used as supports of nickel catalysts for the methane reforming reaction with carbon dioxide to synthesis gas. The structural and textural characteristics of the supports and catalysts are systematically examined by N-2 adsorption/desorption and X-ray diffraction (XRD) techniques. It is found that the pore structures and surface properties of supports greatly affect the catalytic activities of the catalysts prepared. The catalysts supported on the mesoporous clays or pillared clays are obviously superior to those on microporous supports because the mesoporous supports are highly thermal stable compared to the microporous ones. It is found that introducing lanthanum to the supports can improve the catalyst basicity and thus enhance the catalytic activities of these catalysts. Deactivation of catalysts prepared and factors influencing their stability are also discussed. (C) 1998 Academic Press.

Aminotriazines as locking fragments in macrocyclic synthesis

The macrocyclic compounds (6-(4',6'-diamino-1',3',5'-triazinyl)-1,4,6,8,11-pentaazacyclotetradecane)copper(II) triperchlorate dihydrate, [Cu(HL2)](ClO4)(3). 2H(2)O, (6-(6'-amino-4'-oxo-1'H-1',3',5'-triazinyl)-1,4,6,8,11-pentaazacyclotetradecane)copper(II) diperchlorate hydrate, [CuL3](ClO4)(2). H2O, and [(6-(4',6'-dioxo-1'H-1',3',5'-triazinyl) 1,4,6,8,11-pentaazacyclotetradecane)copper(II)] diperchlorate, [CuL4](ClO4)(2), have been synthesized. The macrocycles synthesized contain respectively pendant melamine, ammeline,and ammelide rings. The X-ray cyrstallographic analyses of [Cu(HL2)](ClO4)(3). 2H(2)O, triclinic, space group P (1) over bar, a = 9.489(10) Angstrom, b = 12.340(2) Angstrom, c = 24.496(4) Angstrom, alpha = 87.74(10)degrees beta = 85.51(10)degrees gamma = 70.95(10)degrees and Z = 4, and {[CuL3](ClO4)(2). H2O}2, monoclinic, space group C2/c, a = 18.624(8) Angstrom, b = 17.160(2) Angstrom, c = 15.998(6) Angstrom, beta = 117.82(2)degrees, and Z = 4, are reported. The structure of [Cu(HL2)](ClO4)(3). 2H(2)O shows the formation of linear tapes, formed by a combination of hydrogen bonds and pi-pi stacking interactions. The structure of [CuL3](ClO4)(2). H2O displays formation of dimers, formed by a coordinate bond from the oxygen in one molecule to the copper atom of another. The tautomeric forms of the ammeline and ammelide moieties have been determined. The potential of these compounds as subunits for cocrystallization has been investigated.

Biomolecular interaction analysis of IFN gamma-induced signaling events in whole-cell lysates: Prevalence of latent STAT1 in high-molecular weight complexes

The basic framework for the JAK/STAT pathway is well documented. Recruitment of latent cytoplasmic STAT transcription factors to tyrosine phosphorylated docking sites on cytokine receptors and their JAK-mediated phosphorylation instigates their translocation to the nucleus and their ability to bind DNA, The biochemical processes underlying recruitment and activation of this pathway have commonly been studied in reconstituted in vitro systems using previously defined recombinant signaling components. We have dissected the Interferon gamma (IFN gamma) signal transduction pathway in crude extracts from wild-type and STAT1-negative mutant cell Lines by real-time BIAcore analysis, size-exclusion (SE) chromatography and immune-detection. The data indicate that in detergent-free cell extracts: (1) the phospho-tyrosine (Y440P)-containing peptide motif of the IFN gamma-receptor ct-chain interacts directly with STAT1, or STAT1 complexes, and no other protein; (2) nonactivated STAT 1 is present in a higher molecular weight complex(es) and, at least for IFN gamma-primed cells, is available for recruitment to the activated IFN gamma-receptor from only a subset of such complexes; (3) activated STAT1 is released from the receptor as a monomer.

Erosion/productivity modelling of maize farming in the Philippine uplands part III: Economic analysis of alternative farming methods

Two previous papers in this series (Nelson et al., this issue) described the use of the Agricultural Production Systems Simulator (APSIM) to simulate the effect of erosion on maize yields from open-field farming and hedgerow intercropping in the Philippine uplands. In this paper, maize yields simulated with APSIM are used to compare the economic viability of intercropping maize between leguminous shrub hedgerows with that of continuous and fallow open-field farming of maize. The analysis focuses on the economic incentives of upland farmers to adopt hedgerow intercropping, discussing farmers' planning horizons, access to credit and security of land tenure, as well as maize pricing in the Philippines. Insecure land tenure has limited the planning horizons of upland farmers, and high establishment costs reduce the economic viability of hedgerow intercropping relative to continuous and fallow open-field farming in the short term, In the long term, high discount rates and share-tenancy arrangements in which landlords do not contribute to establishment costs reduce the economic viability of hedgerow intercropping relative to fallow open-field farming, (C) 1998 Elsevier Science Ltd. All rights reserved.

The first structurally characterized discrete dinuclear mu-cyano hexacyanoferrate complex

Mixed valence complexes containing ferro- and ferricyanide have been known for almost 300 years, but no dinuclear, non-polymeric examples of these complexes have been structurally characterized. Here we report the first such example, comprising ferrocyanide coordinated to a pentaaminecobalt(III) complex. This Fe-II-Co-III complex may be reversibly oxidized to the Fe-III-Co-III analogue.

Crystal and molecular structure of 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone (NIH) and its iron(III) complex: an iron chelator with anti-tumour activity

Previous studies have demonstrated that 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone (NIH) and several other aroylhydrazone chelators possess anti-neoplastic activity due to their ability to bind intracellular iron. In this study we have examined the structure and properties of NIH and its Fe-III complex in order to obtain further insight into its anti-tumour activity. Two tridentate NIH ligands deprotonate upon coordination to Fe-III in a meridional fashion to form a distorted octahedral, high-spin complex. Solution electrochemistry of [Fe(NIH-H)(2)](+) shows that the trivalent oxidation state is dominant over a wide potential range and that the Fe-II analogue is not a stable form of this complex. The fact that [Fe(NIH-H)(2)](+) cannot-cycle between the Fe-II and Fe-III states suggests that the production of toxic free- radical species, e.g. OH. or O2(.-),is not part of this ligand's cytotoxic action. This suggestion is supported by cell culture experiments demonstrating that the addition of Fe-III to NIH prevents its anti-proliferative effect. The chemistry of this chelator and its Fe-III complex are discussed in the context of understanding its anti-tumour activity.

The crack tip strain field of AISI 4340 - Part III - Hydrogen influence

This paper studied the influence of hydrogen and water vapour environments on the plastic behaviour in the vicinity of the crack tip for AISI 4340. Hydrogen and water vapour (at a pressure of 15 Torr) significantly increased the crack tip opening displacement. The crack tip strain distribution in 15 Torr hydrogen was significantly different to that measured in vacuum. In the presence of sufficient hydrogen, the plastic zone was larger, was elongated in the direction of crack propagation and moreover there was significant creep. These observations support the hydrogen enhanced localised plasticity model for hydrogen embrittlement in this steel. The strain distribution in the presence of water vapour also suggests that SCC in AISI 4340 occurs via the hydrogen enhanced localised plasticity mechanism. (C) 1999 Kluwer Academic Publishers.

Metal-directed synthesis routes to a 16-membered tetraazamacrocycle with two pendant primary amine groups

The reaction of the bis(propane-1,3-diamine)copper(II) ion with paraformaldehyde and nitroethane in dry methanol under basic conditions produces a macrocyclic product, (cis-3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane)copper(II) perchlorate, in low yield, compared with the good yield obtained in the parallel chemistry possible even under aqueous conditions using palladium(II) as a template. The palladium complex was reduced with zinc amalgam in dilute aqueous acid to yield the metal-free 16-membered macrocyclic hexaamine, in this case re-complexed and characterised by an X-ray crystal structure as the (cis-3,11-dimethyl-1,5,9,13-tetraazacyclohexadecane-3,11-diamine)copper(II) perchlorate. The copper ion is found in a tetragonally elongated and trigonally-distorted octahedral environment, with all six of the ligand nitrogens coordinated, the two primary amine pendant groups occupying cis sites. (C) 2000 Elsevier Science S.A. All rights reserved.

Determination of the stability constants of mercury(II) complexes of mixed donor macrobicyclic encapsulating ligands

The reactions of mercury(II) with the mixed donor encapsulating ligands 3,6,16-trithia-6,11,19-triazabicyclo[6.6.6]icosane (AMN(3)S(3)sar) and 1-amino-8-methyl-6,19-dithia-3,10,13,16-tetraazabicyclo[6.6.6]icosane (AMN(4)S(2)sar) have been studied. NMR ligand-ligand competition experiments with the ligands 1,4,8,11-tetraazaeyclotetradecane ([14]aneN(4)), 1-thia-4,7,10-triazacyclododecane ([12]aneN(3)S) and ethylenediaminetetraacetic acid (EDTA) with AMN(3)S(3)sar and Hg(II) indicated that [14]aneN(4) would be an appropriate competing ligand for the, determination of the Hg(II) stability constant. Calculations indicated the ratio of concentrations of AMN3S3sar, [14]aneN(4) and Hg(II) required for the determination of the stability constant ranged from 1:1:1 to 1:5:1. Refinement of the titration curves yielded log(10)K[Hg(AMN(3)S(3)sar)](2+) = 17.7. A similar competition titration resulted in the determination of the stability constant for the AMN(4)S(2)sar system as log(10)K[Hg(AMN(4)S(2)sar)](2+) = 19.5. The observed binding constants for the mixed N/S donor systems and the hexaaza analogues sar (3,6,10,13,16,19-hexaazabicyclo [6.6.6]icosane) and diamsar (1,8-diamino-3,6,10,13,16,19 -hexazabicyclo [6.6.6] icosane (log(10)K-[Hg(diamsar)](2+) = 26.4; log(10)K[Hg(sar)](2+) = 28.1) differ by approximately ten orders of magnitude. The difference is ascribed not to a cryptate effect but to a mismatch in the Hg-N and Hg-S bond lengths in the N/S systems.

Flexibility revealed by the 1.85 angstrom crystal structure of the beta sliding-clamp subunit of Escherichia coli DNA polymerase III

The beta subunit of the Escherichia coli replicative DNA polymerase III holoenzyme is the sliding clamp that interacts with the alpha (polymerase) subunit to maintain the high processivity of the enzyme. The beta protein is a ring-shaped dimer of 40.6 kDa subunits whose structure has previously been determined at a resolution of 2.5 Angstrom [Kong et al. (1992), Cell, 69, 425-437]. Here, the construction of a new plasmid that directs overproduction of beta to very high levels and a simple procedure for large-scale purification of the protein are described. Crystals grown under slightly modified conditions diffracted to beyond 1.9 Angstrom at 100 K at a synchrotron source. The structure of the beta dimer solved at 1.85 Angstrom resolution shows some differences from that reported previously. In particular, it was possible at this resolution to identify residues that differed in position between the two subunits in the unit cell; side chains of these and some other residues were found to occupy alternate conformations. This suggests that these residues are likely to be relatively mobile in solution. Some implications of this flexibility for the function of beta are discussed.

Brazilian Adaptation of the Woodcock-Johnson III Cognitive Tests

An adaptation of the standard battery of Woodcock-Johnson III Tests of Cognitive Abilities (WJ-III) for Brazilian children and youth was investigated. The sample was composed of 1094 students (54 percent girls), ages 7-17, living in Sao Paulo state (91 percent). Items from Brazilian school books as well as from the WJ-III Spanish version (Bateria-R) were added to comprehension-knowledge tests. Brazilian words were adapted to the auditory tests according to syllabic division and stressed syllables. Items were examined through IRT and age differences through analysis of variance. Results indicated the need to remove items from all WJ-III subtests with the exception of the visual learning test. Analysis of Variance indicated significant age differences (p <= 0.001) for all tests. Thus, the importance of a Brazilian adaptation for the WJ-III was confirmed.