The success of metal‐based anticancer therapeutics in the treatment of cancer is best exemplified by cisplatin. Currently used in 32/78 cancer regimens, metal‐based drugs have a clear role in cancer therapy. Despite this, metal‐based anticancer therapeutics are not without drawbacks, with issues such as toxic side effects and the development of resistance mechanisms. This has led to investigations of other metal‐based drug candidates such as auranofin, a gold‐based drug candidate as well as ruthenium‐based candidates, NAMI‐A, NKP‐1339 and TLD‐1433. All are currently undergoing clinical trials. Another class of complexes under study are rhenium‐based; such complexes have undergone extensive in vitro testing but only nine have been reported to display antitumour in vivo activity, which is a necessary step before entering clinical trials. This review will document, chronologically, the rhenium‐based drug candidates that have undergone in vivo testing and the outlook for such complexes.
The stable isotope compositions of Cu and Zn in major geochemical reservoirs are increasingly studied with the aim to develop these isotope systems as tools to investigate the global biogeochemical cycles of these trace metals. The objectives of the present study were (i) to expand the range of Cu, Zn, and Pb isotope compositions of mineral dust by analyzing samples from major mineral dust sources in Asia and Africa (Chinese Loess Plateau, Chinese deserts, Thar desert, Sahel region) and (ii) to assess the potential impact of human activities on the isotope composition of aerosols by synthesizing published Cu and Zn isotope compositions in aerosols and natural and anthropogenic sources. For the newly analyzed mineral dust areas in Asia and Africa, δ 65 Cu NIST−976 values range from −0.54 to +0.52‰, δ 66 Zn JMC−Lyon values from −0.07 to +0.57‰, and 206 Pb/ 204 Pb values from 18.522 to 19.696. We find a significant geographic control with samples from the Thar Desert having the heaviest isotopic compositions (δ 65 Cu NIST−976 = +0.48 ± 0.06‰, δ 66 Zn JMC−Lyon = +0.49 ± 0.11‰) and samples from the Sahel and the Badain Jaran desert having the lightest Zn isotope composition (δ 66 Zn JMC−Lyon = +0.19 ± 0.15‰ and +0.07 ± 0.07‰, respectively). We find important variations in the isotope signatures between particle size fractions with heavier isotopic compositions in the smallest and largest particle size fractions and lighter isotopic compositions in the mid particle size fractions. Associations with the mineralogical composition are less clear. Newly analyzed aerosol samples for Beijing and Xi'an show δ 65 Cu NIST−976 values of +0.29 ± 0.19‰ and +0.16 ± 0.04‰, δ 66 Zn JMC−Lyon values of −0.36 ± 0.04‰ and +0.02 ± 0.06‰, and 206 Pb/ 204 Pb values of 18.129 ± 0.003 and 18.031 ± 0.003, respectively. Based on a synthesis of published and novel data, we suggest improved ranges and mean values for the isotopic composition of mineral dust from selected locations in Asia and Africa and of anthropogenic sources such as non-exhaust traffic emissions, combustion, electroplating and galvanization. This should serve as a valuable reference for future studies using these isotope systems. This paper demonstrates univocally that human activity introduces a wide range of Zn isotope compositions into the atmospheric environment and, thus, impacts the biogeochemical cycle of Zn.
Six analogous low molecular weight organogelators are comprehensively characterised to investigate the role of small structural modifications on performance.
The application of Pb isotopes to marine geochemistry is currently hindered by challenges associated with the analysis of Pb isotopes in seawater. The current study evaluates the performance of multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements of seawater Pb isotope compositions following Pb separation by either solid-phase extraction with Nobias Chelate PA-1 resin or coprecipitation with Mg(OH) 2 and using either a Pb double spike or external normalization to Tl for mass bias correction. The four analytical combinations achieve results of similar quality when measuring 1−7 ng of seawater Pb, with reproducibilities (two standard deviations, 2SD) of 100−1200 ppm for 206 Pb/ 207 Pb and 208 Pb/ 207 Pb and 300−1700 ppm for ratios involving the minor 204 Pb isotope. All four procedures enable significantly improved sample throughput compared to an established thermal ionization mass spectrometry (TIMS) double-spike method and produce unbiased seawater Pb isotope compositions with similar or improved precision. Nobias extraction is preferable to coprecipitation due to its greater analytical throughput and suitability for analyses of large seawater samples with high Si(OH) 4 contents. The most accurate Pb isotope data are produced following Nobias extraction and double-spike correction as such analyses are least susceptible to matrix effects. However, Nobias extraction with Tl normalization constitutes an attractive alternative as, unlike the double-spike procedure, only a single mass spectrometric measurement is required, which improves analytical throughput and optimizes Pb consumption for analysis. Despite the advantages of solid-phase extraction, coprecipitation represents a useful Pb separation technique for samples with low to moderate Si contents as it is inexpensive, simple to implement, and the data are only marginally less accurate, especially when combined with a Pb double spike for mass bias correction.
Instantaneous gelation: a reactive precursors approach for the near-instant gelation of oil-on-water slicks down to −5 °C.
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