Worldwide comparison of survival from childhood leukaemia for 1995–2009, by subtype, age, and sex (CONCORD-2): a population-based study of individual data for 89 828 children from 198 registries in 53 countries

Background Global inequalities in access to health care are reflected in differences in cancer survival. The CONCORD programme was designed to assess worldwide differences and trends in population-based cancer survival. In this population-based study, we aimed to estimate survival inequalities globally for several subtypes of childhood leukaemia. Methods Cancer registries participating in CONCORD were asked to submit tumour registrations for all children aged 0-14 years who were diagnosed with leukaemia between Jan 1, 1995, and Dec 31, 2009, and followed up until Dec 31, 2009. Haematological malignancies were defined by morphology codes in the International Classification of Diseases for Oncology, third revision. We excluded data from registries from which the data were judged to be less reliable, or included only lymphomas, and data from countries in which data for fewer than ten children were available for analysis. We also excluded records because of a missing date of birth, diagnosis, or last known vital status. We estimated 5-year net survival (ie, the probability of surviving at least 5 years after diagnosis, after controlling for deaths from other causes [background mortality]) for children by calendar period of diagnosis (1995-99, 2000-04, and 2005-09), sex, and age at diagnosis (< 1, 1-4, 5-9, and 10-14 years, inclusive) using appropriate life tables. We estimated age-standardised net survival for international comparison of survival trends for precursor-cell acute lymphoblastic leukaemia (ALL) and acute myeloid leukaemia (AML). Findings We analysed data from 89 828 children from 198 registries in 53 countries. During 1995-99, 5-year agestandardised net survival for all lymphoid leukaemias combined ranged from 10.6% (95% CI 3.1-18.2) in the Chinese registries to 86.8% (81.6-92.0) in Austria. International differences in 5-year survival for childhood leukaemia were still large as recently as 2005-09, when age-standardised survival for lymphoid leukaemias ranged from 52.4% (95% CI 42.8-61.9) in Cali, Colombia, to 91.6% (89.5-93.6) in the German registries, and for AML ranged from 33.3% (18.9-47.7) in Bulgaria to 78.2% (72.0-84.3) in German registries. Survival from precursor-cell ALL was very close to that of all lymphoid leukaemias combined, with similar variation. In most countries, survival from AML improved more than survival from ALL between 2000-04 and 2005-09. Survival for each type of leukaemia varied markedly with age: survival was highest for children aged 1-4 and 5-9 years, and lowest for infants (younger than 1 year). There was no systematic difference in survival between boys and girls. Interpretation Global inequalities in survival from childhood leukaemia have narrowed with time but remain very wide for both ALL and AML. These results provide useful information for health policy makers on the effectiveness of health-care systems and for cancer policy makers to reduce inequalities in childhood survival

Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects

The production of methanol from CO 2 hydrogenation is a promising potential route to a renewable liquid fuel and renewable energy vector. Herein, three distinct routes to make colloidal catalysts based on mixtures of Cu(0) and ZnO nanoparticles (NPs) and using low-temperature organometallic procedures are reported. The colloids are surface coordinated by a phosphinate ligand: dioctylphosphinate ([DOPA] - ), which delivers a high solubility in organic solvents. Further, the synthetic routes allow fine control of the ZnO:Cu and ligand loadings. The catalysts are prepared by mixing s mall NPs (2 nm) of either Cu(0) or air-stable Cu 2 O NPs with ZnO NPs (3 nm), or by the synthesis of Cu(0) in presence of ZnO NPs (ZnO: 2 nm, Cu: 6 nm). The resulting colloidal catalysts are applied in the liquid phase hydrogenation of CO 2 to methanol (210 °C, 50 bar, 3:1 molar ratio of CO 2 :H 2 ). The catalysts typically exhibit 3 times higher rates when compared to a heterogeneous Cu-ZnO-Al 2 O 3 commercial catalyst (21 vs. 7 mmol MeOH g CuZnO -1 h -1 ). The characterisation of the post-catalysis colloids show clear Cu/ZnO interfaces (HR-TEM), which are formed under reducing conditions, as well as differences in the Cu(0) NP size (from 3 to 7 nm) and nanoscale restructuring of the catalysts. The combination of characterisation and catalytic results indicate that the activity is mostly dictated by the Cu(0) particle size and ligand loading. Smaller Cu(0) NPs exhibited lower turnover frequency (TOF) values, whereas higher ligand loadings ([DOPA] - :(Cu + Zn) of 0.2-1.1) lead to smaller Cu(0) NPs and reduce the formation of Cu/ZnO interfaces. UV-vis spectroscopy reveals that the Cu(0) NPs are more stable to oxidation under air after catalysis than beforehand, potentially due to migration of ZnO onto the Cu surface whilst under catalytic conditions

Layered zinc hydroxide monolayers by hydrolysis of organozincs

2D inorganic materials and their exfoliated counterparts are both of fundamental interest and relevant for applications including catalysis, electronics and sensing. Here, a new bottom-up synthesis route is used to prepare functionalised nanoplatelets, in apolar organic solvents, via the hydrolysis of organometallic reagents; the products can be prepared in high yield, at room temperature. In particular, a series of layered zinc hydroxides, coordinated by aliphatic carboxylate ligands, were produced by the hydrolysis of diethyl zinc and zinc carboxylate mixtures, optimally at a molar ratio of [COOR]/[Zn] = 0.6. Layered zinc hydroxides coordinated by oleate ligands form high concentration solutions of isolated monolayers (3 nm thick x ∼ 26 nm) in apolar organic solvents (up to 23 mg mL -1 in toluene), as confirmed by both atomic force and transmission electron microscopies of deposited species. The high solubility of the product allows the synthetic pathway to be monitored directly in situ through 1 H NMR spectroscopy. The high solubility also provides a route to solution deposition of active functional materials, as illustrated by the formation of nanoporous films of optically transparent porous zinc oxide (1 μm thickness) after annealing at 500 °C. This new organometallic route to 2D materials obviates common complications of top-down exfoliation syntheses, including sonochemical-degradation and low yields of aggregated polydispersed layers, and may potentially be extended to a wide range of systems

Correction: Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects

The production of methanol from CO2 hydrogenation is a promising potential route to a renewable liquid fuel and renewable energy vector. Herein, three distinct routes to make colloidal catalysts based on mixtures of Cu(0) and ZnO nanoparticles (NPs) and using low-temperature organometallic procedures are reported. The colloids are surface coordinatedy by a phosphinate ligand: Dioctylphosphinate ([DOPA]−), which delivers a high solubility in organic solvents. Further, the synthetic routes allow fine control of the ZnO:Cu and ligand loadings. The catalysts are prepared by mixing small NP (2 nm) of either Cu(0) or air-stable Cu2O NPs with ZnO NPs (3 nm), or by the synthesis of Cu(0) in presence of ZnO NPs (ZnO: 2 nm, Cu: 6 nm). The resulting colloidal catalysts are applied in the liquid phase hydrogenation of CO2 to methanol (210°C, 50 bar, 3:1 molar ratio of CO2:H2). The catalysts typically exhibit 3 times higher rates when compared to a heterogeneous Cu-ZnO-Al2O3 commercial catalyst (21 vs 7 mmolMeOH.gCuZnO-1.h-1). The characterisation of the post-catalysis colloids show clear Cu/ZnO interfaces (HR-TEM), which are formed under reducing conditions, as well as differences in the Cu(0) NP size (from 3 to 7 nm) and nanoscale restructuring of the catalysts. The combination of characterisation and catalytic results indicate that the activity is mostly dictated by the Cu(0) particle size and ligand loading. Smaller Cu(0) NPs exhibited lower turnover frequency (TOF) values, whereas higher ligand loadings ([DOPA]−:(Cu+Zn) of 0.2-1.1) lead to smaller Cu(0) NPs and reduce the formation of Cu/ZnO interfaces. UV-Vis spectroscopy reveals that the Cu(0) NPs are more stable to oxidation under air after catalysis than beforehand, potentially due to migration of ZnO onto the Cu surface whilst under catalytic conditions

Binuclear β-diketiminate complexes of copper(I)

The reaction of a series of dinucleating bis(β-diketiminate) pro-ligands with mesitylcopper in the presence and absence of mono and diphosphines has allowed the isolation of a new series of dicopper(I) complexes. Inclusion of trans-1,2-cyclohexyl (1), 2,6-pyridyl (2), and 2,2′-oxydiaryl (3) spacers between the β-diketiminate units has been studied. The isolation of three new copper(I) phosphine complexes [1·Cu2(PPh3)2], [2·Cu2(PPh3)2] and [3·Cu2(PPh3)2] is reported. While these compounds display large Cu⋯Cu separations of 5.4–7.9 Å in the solid state, solution data are consistent with a large degree of conformational freedom. Modification of the monophosphine to a diphosphine, DPPE, allowed the isolation of the novel 11-membered bimetallic macrocycle [2·Cu2(DPPE)] containing both a binucleating nitrogen based ligand and a chelating diphosphine. While acetonitrile adducts of this series could also be generated in situ, under forcing conditions reaction of the 2,6-pyridyl bridged ligand with mesityl copper led to the formation [2·Cu2]2. This latter complex is a dimer of dicopper(I) units in which the bis(β-diketiminate) ligand now binds four copper(I) centers through not only the expected κ2-N,N′-chelation but also κ1- and η2-binding of the central pyridine through orthogonal Cu–N and Cu–arene interactions. Reversible coordination of alkenes, pyridine and quinoline to the copper cluster was identified allowing the isolation and structural characterisation of a further series of dinuclear complexes [2·Cu2(pyridine)2], [2·Cu2(cyclopentene)2] and [2·Cu2(norbornene)2]. Solution studies allow quantification of the reversible binding event through a van't Hoff analysis. Both solution and the solid state data suggest a weak anagostic interaction exists in the latter two alkene complexes of copper(I). The new complexes have been characterized by X-ray diffraction, multinuclear NMR spectroscopy and CHN analysis

Cu/M:ZnO (M = Mg, Al, Cu) colloidal nanocatalysts for the solution hydrogenation of carbon dioxide to methanol

Doped-ZnO nanoparticles, capped with dioctylphosphinate ligands, are synthesised by the controlled hydrolysis of a mixture of organometallic precursors. Substitutional doping of the wurtzite ZnO nanoparticles with 5 mol% Mg(II), Al(III) and Cu(I) is achieved by the addition of sub-stoichiometric amounts of the appropriate dopant [(n-butyl)(sec-butyl)magnesium, triethylaluminium or mesitylcopper] to diethylzinc in the precursor mixture. After hydrolysis, the resulting colloidal nanoparticles (sizes of 2–3 nm) are characterised by powder X-ray crystallography, transmission electron microscopy, inductively-coupled plasma optical emission spectrometry and X-ray photoelectron spectroscopy. A solution of the doped-ZnO nanoparticles and colloidal Cu(0) nanoparticles [M:ZnO : Cu = 1 : 1] are applied as catalysts for the hydrogenation of CO2 to methanol in a liquid-phase continuous flow stirred tank reactor [210 °C, 50 bar, CO2 : H2 = 1 : 3, 150 mL min−1, mesitylene, 20 h]. All the catalyst systems display higher rates of methanol production and better stability than a benchmark heterogeneous catalyst, Cu–ZnO–Al2O3 [480 μmol mmolmetal−1 h−1], with approximately twice the activity for the Al(III)-doped nanocatalyst. Despite outperforming the benchmark catalyst, Mg(II) doping is detrimental towards methanol production in comparison to undoped ZnO. X-Ray photoelectron spectroscopy and transmission electron microscopy analysis of the most active post-catalysis samples implicate the migration of Al(III) to the catalyst surface, and this surface enrichment is proposed to facilitate stabilisation of the catalytic ZnO/Cu interfaces

Cu/M:ZnO (M = Mg, Al, Cu) colloidal nanocatalysts for the solution hydrogenation of carbon dioxide to methanol

Doped-ZnO nanoparticles, capped with dioctylphosphinate ligands, are synthesised by the controlled hydrolysis of a mixture of organometallic precursors. Substitutional doping of the wurtzite ZnO nanoparticles with 5 mol% Mg(II), Al(III) and Cu(I) is achieved by the addition of sub-stoichiometric amounts of the appropriate dopant [(n-butyl)(sec-butyl)magnesium, triethylaluminium or mesitylcopper] to diethylzinc in the precursor mixture. After hydrolysis, the resulting colloidal nanoparticles (sizes of 2–3 nm) are characterised by powder X-ray crystallography, transmission electron microscopy, inductively-coupled plasma optical emission spectrometry and X-ray photoelectron spectroscopy. A solution of the doped-ZnO nanoparticles and colloidal Cu(0) nanoparticles [M:ZnO : Cu = 1 : 1] are applied as catalysts for the hydrogenation of CO2 to methanol in a liquid-phase continuous flow stirred tank reactor [210 °C, 50 bar, CO2 : H2 = 1 : 3, 150 mL min−1, mesitylene, 20 h]. All the catalyst systems display higher rates of methanol production and better stability than a benchmark heterogeneous catalyst, Cu–ZnO–Al2O3 [480 μmol mmolmetal−1 h−1], with approximately twice the activity for the Al(III)-doped nanocatalyst. Despite outperforming the benchmark catalyst, Mg(II) doping is detrimental towards methanol production in comparison to undoped ZnO. X-Ray photoelectron spectroscopy and transmission electron microscopy analysis of the most active post-catalysis samples implicate the migration of Al(III) to the catalyst surface, and this surface enrichment is proposed to facilitate stabilisation of the catalytic ZnO/Cu interfaces