Peter Leverett

Dispersion of antimony from oxidizing ore deposits

The solubilities of brandholzite, [Mg(H2O)6][Sb(OH)6]2, and bottinoite, [Ni(H2O)6][Sb(OH)6]2, at 25 °C in water have been measured. Solubilities are 1.95(4) × 10-3 and 3.42(11) × 10-4 mol dm-3, respectively. The incongruent dissolution of romeite, Ca2Sb2O7, and bindheimite, Pb2Sb2O7, at 25 °C in 0.100 mol dm-3 aqueous HNO3 was also investigated. Equilibrium dissolved Sb concentrations were 3.3 ± 1.0 × 10-7 and 7.7 ± 2.1 × 10-8 mol dm-3, respectively. These values have been used to re-evaluate the geochemical mobility of Sb in the supergene environment. It is concluded that the element is geochemically immobile in solution and in soils. This was in part validated by an orientation soil geochemical survey over the Bayley Park prospect near Armidale, New South Wales, Australia. Anomalous soil Sb levels are confined to within 100 m of known stibnite mineralization.

Raman spectroscopy of basic copper(II) and some complex copper(II) sulfate minerals: Implications for hydrogen bonding

Abstract Raman spectroscopy has been applied to the study of basic Cu sulfates including antlerite, brochiantite, posnjakite, langite, and wroewolfeite and selected complex Cu sulfate minerals. Published X-ray diffraction data were used to estimate possible hydrogen bond distances for the basic Cu sulfate minerals. A Libowitzky empirical expression was used to predict hydroxyl-stretching frequencies and agreement with the observed values was excellent. This type of study was then extended to complex basic Cu sulfates: cyanotrichite, devilline, glaucocerinite, serpierite, and ktenasite. The position of the hydroxyl-stretching vibration was used to estimate the hydrogen bond distances between the OH and the SO4 units. The variation in bandwidth of the OH-stretching bands provided an estimate of the variation in these hydrogen bond distances. By plotting the hydrogen bond O…O distance as a function of the position of the SO4 symmetric stretching vibration, the position of the SO4 symmetric stretching band was found to be dependent upon the hydrogen bond distance for both the basic Cu sulfates and the complex Cu sulfates.

Vibrational spectroscopy of the basic copper phosphate minerals: pseudomalachite, ludjibaite and reichenbachite

The vibrational spectra of pseudomalachite, reichenbachite and ludjibaite have been obtained at 298 K using a combination of FTIR and Raman microscopy. The vibrational spectra of the minerals are different, in line with differences in crystal structure and composition. Some similarity in the Raman spectra of the three polymorphs pseudomalachite, reichenbachite and ludjibaite exists, particularly in the OH stretching region, but characteristic differences in the OH deformation regions are observed. Differences are also observed in the phosphate stretching and deformation regions.

The antimicrobial properties of some copper(II) and platinum(II) 1,10-phenanthroline complexes

Copper(II) (1(Cu)-21(Cu)) and previously established experimental anticancer platinum(II) metallointercalator complexes (1(Pt)-16(Pt)) have been prepared and investigated for their antimicrobial properties. These complexes are of the general structure [M(I(L))(A(L))](2+) where I(L) represents functionalised 1,10-phenanthrolines (1(IL)-10(IL)), and A(L) represents 1,2-diaminoethane, 1S,2S- or 1R,2R-diaminocyclohexane. The structures of synthesised complexes were confirmed using a combination of elemental analysis, UV spectrometry, circular dichroism, (1)H and [(1)H-(195)Pt]-HMQC NMR, X-ray crystallography, and electrospray ionisation mass spectrometry and where appropriate. Crystallisation attempts yielded single crystals of [Cu(4-methyl-1,10-phenanthroline)(1R,2R-diaminocyclohexane)](ClO(4))(2) (4(Cu)), [Cu(5,6-dimethyl-1,10-phenanthroline)(1R,2R-diaminocyclohexane)(H(2)O)](ClO(4))(2)·1.5H(2)O (10(Cu)) and [Cu(5,6-dimethyl-1,10-phenanthroline)(3)](ClO(4))(2)·5,6-dimethyl-1,10-phenanthroline·2H(2)O (21(Cu)). Growth inhibition of liquid cultures of bacteria (Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa), and yeast (Saccharomyces cerevisiae) discerned the most antimicrobially potent metal complexes ≤20 μM, as well as that of their intercalating ligands alone. To further investigate their mode of antimicrobial activity, membrane permeabilisation caused by selected complexes was visualised by means of a cell viability kit under fluorescence microscopy.

Tripuhyite and schafarzikite: two of the ultimate sinks for antimony in the natural environment

Abstract Studies of the stability of the oxides schafarzikite, FeSb2O4, and tripuhyite, FeSbO4, have been undertaken to clarify the roles these secondary minerals may have in determining the dispersion of antimony in oxidizing environments. Solubilities were determined at 298.15 K in aqueous HNO3, and these data were used to calculate values of ∆Gf⊖ at the same temperature. The derived ∆Gf⊖(s, 298.15 K) values for FeSb2O4 and FeSbO4 are −959.4±4.3 and −836.8±2.2 kJ mol−1, respectively. These results have been compared with electrochemically derived data, extrapolated from 771−981 K. The present study shows conclusively that although the mobility of Sb above the water table is limited by simple Sb(III) and Sb(V) oxides and stibiconite-group minerals, depending upon the prevailing redox potential and pH, tripuhyite is an important ultimate sink for Sb in the supergene environment. It is highly insoluble even in strongly acidic conditions and its anomalous stability at ambient temperatures causes the common mineral goethite, FeOOH, to react to form tripuhyite at activities of Sb(OH)5(aq) as low as 10−11. The comparatively limited numbers of reported occurrences of tripuhyite in the supergene zone are almost certainly due to the fact that its physical properties, especially colour and habit, are remarkably similar to those of goethite. In contrast, the small number of reported occurrences of schafarzikite can be related to its decomposition to tripuhyite as redox potentials rise at the top of the supergene zone and the fact that it decomposes to sénarmontite, Sb2O3, in acidic conditions, releasing Fe2+ ions into solution. In general, the findings confirm the immobility of Sb in near-surface conditions. Geochemical settings favouring the formation of the above minerals have been assessed using the results of the present study and data from the literature.

Cytotoxic platinum(II) intercalators that incorporate 1R,2R-diaminocyclopentane

Twelve metallointercalators of the type [Pt(I(L))(A(L))](2+), where A(L) is either the R,R or S,S enantiomer of 1,2-diaminocyclopentane (DACP) and I(L) is either 1,10-phenathroline, 4-methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline or 3,4,7,8-tetramethyl-1,10-phenanthroline, were synthesised, characterised and the cytotoxicity to the L1210 cell line was determined. The crystal structures of PHENRRDACP and PHENSS were obtained as monoclinic with a space group of P2(1) (a/Å = 11.4966, b/Å = 6.6983, c/Å = 12.0235) and P2(1) (a/Å = 11.5777, b/Å = 7.0009, c/Å = 12.5079), respectively. The R,R enantiomer of 1,2-diaminocyclopentane (RRDACP) produced the most cytotoxic metallointercalators. The most cytotoxic metallointercalators were 56MERRDACP and 47MERRDACP with IC(50) values of 0.16 and 0.17 μM, respectively, in comparison to cisplatin (1 μM).

Copper(ii) and palladium(ii) complexes with cytotoxic and antibacterial activity

The synthesis of eight square pyramidal copper complexes with general structure [Cu(IL)(AL)H2O]2+, where IL represents various methylated 1,10-phenanthrolines, and AL represents either 1S,2S- or 1R,2R-diaminocyclohexane, is reported, with the complexes synthesised as both the perchlorate and chloride salts. The crystal structures of [Cu(1,10-phenanthroline)(1S,2S-diaminocyclohexane](ClO4)2·H2O and [Cu(5,6-dimethyl-1,10-phenanthroline)(1S,2S-diaminocyclohexane](ClO4)2·1.5H2O are reported. Four square planar palladium complexes with general structure [Pd(IL)(AL)]Cl2 have also been synthesised. These complexes were synthesised in order to investigate the structure–activity relationship against both cancer cell lines and bacterial cultures. The copper complexes display anticancer activity similar to cisplatin and 1,10-phenanthroline (phen) in the L1210 murine leukaemia cell line. Methylation of the phen increased the copper complex cytotoxicity by approximately four-fold, compared with the non-methylated complex. No significant difference in activity was observed by altering the chirality of the diaminocyclohexane ligand. The copper complexes demonstrated antibacterial activity against Bacillus subtilis, Staphylococcus aureus, and Escherichia coli; however, high levels of toxicity (30–60 % of death) were observed in the nematode Caenorhabditis elegans. The copper complexes have also been shown to act as DNA nucleases, with the ability to cleave plasmid DNA in the presence of hydrogen peroxide. The palladium complexes all have half maximal inhibitory concentration (IC50) values of ~10 μM in the L1210 cell line, with no significant difference in the cytotoxicity of any of the compounds tested. Minimal antibacterial activity of the palladium complexes was observed.

Hoganite and paceite : two new acetate minerals from the Potosi mine, Broken Hill, Australia

Abstract Hoganite, copper(II) acetate monohydrate, and paceite (pronounced ‘pace-ite’), calcium(II) copper(II) tetraacetate hexahydrate, occur as isolated crystals embedded in ferruginous gossan from the Potosi Pit, Broken Hill, New South Wales, Australia. They are associated with goethite, hematite, quartz, linarite, malachite, azurite, cerussite and cuprian smithsonite. Hoganite is bluish green with a pale blue streak and a Mohs hardness of 1½; it possesses perfect {001} and distinct {110} cleavages and has a conchoidal fracture. Chemical analysis of hoganite gave (wt.%) C 23.85; H 3.95; Cu 31.6; Fe 0.4; O (by difference) 40.2, yielding an empirical formula of C4H7.89O5.07Cu1.00Fe0.01. The simplified formula is C4H8O5Cu or Cu(CH3COO)2. H2O, the mineral being identical to the synthetic compound of the same formula. Single-crystal X-ray data for hoganite are: monoclinic, space group C2/c, α = 13.162(3), b = 8.555(2), c = 13.850(3) Å, β = 117.08(3)°, Z = 8. The density, calculated from single-crystal data, is 1.910 g cm-3. The strongest lines in the X-ray powder pattern are [dobs (Iobs) (hkl)] 6.921 (100) (011); 3.532 (28) (202); 6.176 (14) (200); 3.592 (11) (1̅22); 5.382 (10) (2̅11); 2.278 (10) (204); 5.872 (9) (002). Hoganite (orientation presently unknown) is biaxial positive with α = 1.533(2), β = 1.541(3), γ = 1.554(2), 2V(meas.) = 85(5)°, 2V(calc.) = 76.8°, dispersion is r < v, medium (white light); it is strongly pleochroic with X = blue, Y = pale bluish, Z = pale bluish green and absorption X > Y > Z. The mineral is named after Graham P. Hogan of Broken Hill, New South Wales, Australia, a miner and well-known collector of Broken Hill minerals. Paceite is dark blue with a pale blue streak and a Mohs hardness of 1½; it possesses perfect {100} and {110} cleavages and has an uneven fracture. Chemical analysis of paceite gave (wt.%) C 21.25; H 5.3; Ca 9.0; Cu 14.1; O (by difference) 50.35, yielding an empirical formula of C8H23.77O14.23Ca1.02-Cu1.00. The simplified formula is C8H24O14CaCu or CaCu(CH3COO)4. 6H2O, the mineral being identical to the synthetic compound of the same formula. Unit-cell data (refined from X-ray powder diffraction data) for paceite are: tetragonal, space group I4/m, α = 11.155(4), c = 16.236(17) Å, Z = 4. The density, calculated from refined cell data, is 1.472 g cm-3. The strongest lines in the X-ray powder pattern are [dobs (Iobs) (hkl)] 7.896 (100) (110); 3.530 (20) (310); 5.586 (15) (200); 8.132 (8) (002); 9.297 (6) (101); 2.497 (4) (420); 3.042 (3) (321). Paceite is uniaxial positive with ω = 1.439(2) and ε = 1.482(3) (white light); pleochroism is bluish with a greenish tint (O), pale bluish with a greyish tint (E), and absorption O ≥ E. The mineral is named after Frank L. Pace of Broken Hill, New South Wales, Australia, an ex-miner and well-known collector of Broken Hill minerals.

The structure of H3O+-exchanged pharmacosiderite

Abstract The crystal structure of H3O+-exchanged pharmacosiderite (pharmacosiderite is KFe4(AsO4)3(OH)4·nH2O, sensu stricto) has been determined by single-crystal X-ray diffraction and refined to R1 = 0.0418. H3O+-exchanged pharmacosiderite, (H3O+)Fe4(AsO4)3(OH)4·4.5H2O, is cubic, space group P4̄3m, with a = 7.982(9) Å, V = 508.5(9) Å3 and Z = 1. The structure broadly conforms to that of the general pharmacosiderite structure type, with the hydronium ion generated by partial protonation of a site corresponding to a molecule of water of crystallization and its symmetry-related equivalents. In addition, the structure of a “pharmacosiderite″ from Cornwall, United Kingdom, in which no alkali metals could be detected, has been re-evaluated and found to be consistent with that of the H3O+- exchanged structure. Its composition is (H3O+)Fe4(AsO4)3(OH)4·4H2O, with the partially occupied water found for the exchanged structure at (½, ½, ½) being absent in this case.

Paratacamite-(Mg), Cu3(Mg,Cu)Cl2(OH)6; a new substituted basic copper chloride mineral from Camerones, Chile

Abstract Paratacamite-(Mg) (IMA 2013-014), Cu3(Mg,Cu)Cl2(OH)6, is the new Mg-analogue of paratacamite. It was found near the village of Cuya in the Camarones Valley, Arica Province, Chile. The mineral is a supergene secondary phase occurring in association with anhydrite, atacamite, chalcopyrite, copiapite, dolomite, epsomite, haydeeite, hematite, magnesite and quartz. Paratacamite-(Mg) crystals are rhombs and thick to thin prisms up to 0.3 mm in size exhibiting the forms {201} and {001}. Twinning by reflection on {101̅} is common. The mineral is transparent with a vitreous lustre, with medium to deep-green colour and light-green streak. Mohs hardness is 3-3½, the tenacity is brittle and the fracture is conchoidal. Paratacamite-(Mg) has one perfect cleavage on {201}. The measured and calculated densities are 3.50(2) and 3.551 g cm-3, respectively. The mineral is optically uniaxial (-) with Ɛ = 1.785(5) and ω > 1.8 and slight pleochroism: O (bluish green) > E (green). Electron-microprobe analyses provided the empirical formula Cu3(Mg0.60Cu0.38Ni0.01Mn0.01)Cl2(OH)6. The mineral is easily soluble in dilute HCl. Paratacamite- (Mg) is trigonal, R3̅, with cell parameters a = 13.689(1), c = 14.025(1) Å, V = 2275.8(3) Å3 and Z = 12. There is a pronounced sub-cell corresponding to a’ ≈ ½a, c’ ≈ c in space group R3̅m. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 5.469(87)(021), 4.686(26)(003), 2.904(34)(401), 2.762(100)(223̅,042), 2.265(81)(404), 1.819(26)(603), 1.710 (34)(440) and 1.380(19)(446). The structure was refined to R1 = 0.039 for 480 Fo > 4σF reflections. Refinement using interlayer Mg-Cu site scattering factors indicated that Mg is distributed statistically between both interlayer octahedra M1O6 and M2O6. A comparison of the distortions associated with M1O6 and M2O6 octahedra suggest that the sample is near the upper compositional limit for stability of the R3̅ phase.