Platinum(II) compounds containing cyclometalated tridentate ligands: Synthesis, luminescence studies, and a selective fluoro for methoxy substitution

Two series of potentially tridentate ligands of formula ArCH=N(CH2)2NMe2 and ArCH=N(CH2)3NMe2 (Ar = C6H5, 2-FC6H4, 4-FC6H4, 2,3,4-F3C6H2) were used to prepare [C,N,N′]-cyclometalated platinum compounds containing either a chloro or a methyl ancillary ligand. The synthesis of the compounds [PtCl{Me2N(CH2)xN=CHR}] (3a−h), via the corresponding compounds [PtCl2{Me2N(CH2)xN=CHAr}] (2), requires drastic conditions and proceeds more easily for ligands derived from N,N-dimethylpropylenediamine (x = 3). Along the process, an unexpected selective nucleophilic substitution of a fluoro for a methoxy substituent took place at the aryl ring for ligands 2,3,4-F3C6H2CH=N(CH2)xNMe2. The syntheses of compounds [PtMe{Me2N(CH2)xN=CHR}] (4a−h) using [Pt2Me4(μ-SMe2)2] as a precursor took place for all ligands under relatively mild conditions. All compounds were fully characterized, including molecular structure determination for [PtCl{Me2N(CH2)3N=CH(4-FC6H3)}] (3b) and [PtCl{Me2N-(CH2)3N=CH(2-OMe,3,4-F2C6H)}] (3g). The absorption and emission spectra were also studied for the [C,N,N′]-cyclometalated platinum(II) compounds, and all of the compounds were emissive in the solid state and in dichloromethane solution at room temperature (compounds 3) or at 77 K (compounds 4). The size of the [N,N′]-chelate ring and the number and position of the substituents in the aryl ring modulate the intensity and the energy of the emission

Platinum(II) Compounds Containing Cyclometalated Tridentate Ligands: Synthesis, Luminescence Studies, and a Selective Fluoro for Methoxy Substitution

Two series of potentially tridentate ligands of formula ArCHN­(CH₂)₂NMe₂ and ArCHN­(CH₂)₃NMe₂ (Ar = C₆H₅, 2-FC₆H₄, 4-FC₆H₄, 2,3,4-F₃C₆H₂) were used to prepare [C,N,N′]-cyclometalated platinum compounds containing either a chloro or a methyl ancillary ligand. The synthesis of the compounds [PtCl­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>3a</b>–<b>h</b>), via the corresponding compounds [PtCl₂{Me₂N­(CH₂)_<i>x</i>NCHAr}] (<b>2</b>), requires drastic conditions and proceeds more easily for ligands derived from <i>N</i>,<i>N</i>-dimethylpropylenediamine (<i>x</i> = 3). Along the process, an unexpected selective nucleophilic substitution of a fluoro for a methoxy substituent took place at the aryl ring for ligands 2,3,4-F₃C₆H₂CHN­(CH₂)_<i>x</i>NMe₂. The syntheses of compounds [PtMe­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>4a</b>–<b>h</b>) using [Pt₂Me₄(μ-SMe₂)₂] as a precursor took place for all ligands under relatively mild conditions. All compounds were fully characterized, including molecular structure determination for [PtCl­{Me₂N­(CH₂)₃NCH­(4-FC₆H₃)}] (<b>3b</b>) and [PtCl­{Me₂N­(CH₂)₃NCH­(2-OMe,3,4-F₂C₆H)}] (<b>3g</b>). The absorption and emission spectra were also studied for the [C,N,N′]-cyclometalated platinum­(II) compounds, and all of the compounds were emissive in the solid state and in dichloromethane solution at room temperature (compounds <b>3</b>) or at 77 K (compounds <b>4</b>). The size of the [N,N′]-chelate ring and the number and position of the substituents in the aryl ring modulate the intensity and the energy of the emission

Platinum(II) Compounds Containing Cyclometalated Tridentate Ligands: Synthesis, Luminescence Studies, and a Selective Fluoro for Methoxy Substitution

Two series of potentially tridentate ligands of formula ArCHN­(CH₂)₂NMe₂ and ArCHN­(CH₂)₃NMe₂ (Ar = C₆H₅, 2-FC₆H₄, 4-FC₆H₄, 2,3,4-F₃C₆H₂) were used to prepare [C,N,N′]-cyclometalated platinum compounds containing either a chloro or a methyl ancillary ligand. The synthesis of the compounds [PtCl­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>3a</b>–<b>h</b>), via the corresponding compounds [PtCl₂{Me₂N­(CH₂)_<i>x</i>NCHAr}] (<b>2</b>), requires drastic conditions and proceeds more easily for ligands derived from <i>N</i>,<i>N</i>-dimethylpropylenediamine (<i>x</i> = 3). Along the process, an unexpected selective nucleophilic substitution of a fluoro for a methoxy substituent took place at the aryl ring for ligands 2,3,4-F₃C₆H₂CHN­(CH₂)_<i>x</i>NMe₂. The syntheses of compounds [PtMe­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>4a</b>–<b>h</b>) using [Pt₂Me₄(μ-SMe₂)₂] as a precursor took place for all ligands under relatively mild conditions. All compounds were fully characterized, including molecular structure determination for [PtCl­{Me₂N­(CH₂)₃NCH­(4-FC₆H₃)}] (<b>3b</b>) and [PtCl­{Me₂N­(CH₂)₃NCH­(2-OMe,3,4-F₂C₆H)}] (<b>3g</b>). The absorption and emission spectra were also studied for the [C,N,N′]-cyclometalated platinum­(II) compounds, and all of the compounds were emissive in the solid state and in dichloromethane solution at room temperature (compounds <b>3</b>) or at 77 K (compounds <b>4</b>). The size of the [N,N′]-chelate ring and the number and position of the substituents in the aryl ring modulate the intensity and the energy of the emission

Platinum(II) Compounds Containing Cyclometalated Tridentate Ligands: Synthesis, Luminescence Studies, and a Selective Fluoro for Methoxy Substitution

Two series of potentially tridentate ligands of formula ArCHN­(CH₂)₂NMe₂ and ArCHN­(CH₂)₃NMe₂ (Ar = C₆H₅, 2-FC₆H₄, 4-FC₆H₄, 2,3,4-F₃C₆H₂) were used to prepare [C,N,N′]-cyclometalated platinum compounds containing either a chloro or a methyl ancillary ligand. The synthesis of the compounds [PtCl­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>3a</b>–<b>h</b>), via the corresponding compounds [PtCl₂{Me₂N­(CH₂)_<i>x</i>NCHAr}] (<b>2</b>), requires drastic conditions and proceeds more easily for ligands derived from <i>N</i>,<i>N</i>-dimethylpropylenediamine (<i>x</i> = 3). Along the process, an unexpected selective nucleophilic substitution of a fluoro for a methoxy substituent took place at the aryl ring for ligands 2,3,4-F₃C₆H₂CHN­(CH₂)_<i>x</i>NMe₂. The syntheses of compounds [PtMe­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>4a</b>–<b>h</b>) using [Pt₂Me₄(μ-SMe₂)₂] as a precursor took place for all ligands under relatively mild conditions. All compounds were fully characterized, including molecular structure determination for [PtCl­{Me₂N­(CH₂)₃NCH­(4-FC₆H₃)}] (<b>3b</b>) and [PtCl­{Me₂N­(CH₂)₃NCH­(2-OMe,3,4-F₂C₆H)}] (<b>3g</b>). The absorption and emission spectra were also studied for the [C,N,N′]-cyclometalated platinum­(II) compounds, and all of the compounds were emissive in the solid state and in dichloromethane solution at room temperature (compounds <b>3</b>) or at 77 K (compounds <b>4</b>). The size of the [N,N′]-chelate ring and the number and position of the substituents in the aryl ring modulate the intensity and the energy of the emission

Measurement of concentrations of four chemical ultraviolet filters in human breast tissue at serial locations across the breast

The human population is widely exposed to benzophenone-3 (BP-3), octylmethoxycinnamate (OMC), 4-methylbenzilidenecamphor (4-MBC) and homosalate from their use in consumer goods to absorb ultraviolet (UV) light. Their oestrogenic activity and presence in human milk suggest a potential to influence breast cancer development. In this study, high-performance liquid chromatography-tandem mass spectrometry was used to measure concentrations of these UV filters in human breast tissue from three serial locations across the breast from 40 women undergoing mastectomy for primary breast cancer. One or more of these UV filters were quantifiable in 101 of 120 (84%) of the tissue samples and at least one breast region for 38 of 40 women. BP-3 was measured in 83 of 120 (69%) tissue samples and at least one breast region for 33 of 40 women (range 0-26.0 ng g tissue). OMC was measured in 89 of 120 (74%) tissue samples and at least one breast region for 33 of 40 women (range 0-58.7 ng g tissue). 4-MBC was measured in 15 of 120 (13%) tissue samples and at least one breast region for seven of 40 women (range 0-25.6 ng g tissue). Homosalate was not detected in any sample. Spearman's analyses showed significant positive correlations between concentrations of BP-3 and OMC in each of the three breast regions. For ethical reasons cancerous tissue was not available, but as the location of the cancer was known, Mann-Whitney U-tests investigated any link between chemical concentration and whether a tumour was present in that region or not. For the lateral region, more BP-3 was measured when a tumour was present (P = .007) and for OMC the P value was .061. For seven (of 40) women with measurable 4-MBC, six of seven had measurable 4-MBC at the site of the tumour. [Abstract copyright: Copyright © 2018 John Wiley & Sons, Ltd.

Effects of exposure to six chemical ultraviolet filters commonly used in personal care products on motility of MCF-7 and MDA-MB-231 human breast cancer cells in vitro

Benzophenone (BP)-1, BP-2, BP-3, octylmethoxycinnamate (OMC), 4-methylbenzilidenecamphor and homosalate are added to personal care products to absorb ultraviolet light. Their presence in human milk and their oestrogenic activity suggests a potential to influence breast cancer development. As metastatic tumour spread is the main cause of breast cancer mortality, we have investigated the effects of these compounds on migration and invasion of human breast cancer cell lines. Increased motility of oestrogen-responsive MCF-7 human breast cancer cells was observed after long-term exposure (>20 weeks) to each of the six compounds at ≥10−7 m concentrations using three independent assay systems (scratch assay, live cell imaging, xCELLigence technology) and increased invasive activity was observed through matrigel using the xCELLigence system. Increased motility of oestrogen-unresponsive MDA-MB-231 human breast cancer cells was observed after 15 weeks of exposure to each of the six compounds by live cell imaging and xCELLigence technology, implying the increased migratory activity was not confined to oestrogen-responsive cells. Molecular mechanisms varied between compounds and cell lines. Using MCF-7 cells, reduction in E-cadherin was observed following 24 weeks' exposure to 10−5 m BP-1 and 10−5 m homosalate, and reduction in β-catenin was noted following 24 weeks' exposure to 10−5 m OMC. Using MDA-MB-231 cells, increased levels of matrix metalloproteinase 2 were observed after 15 weeks exposure to 10−7 m OMC and 10−7 m 4-methylbenzilidenecamphor. Although molecular mechanisms differ, these results demonstrate that exposure to any of these six compounds can increase migration and invasion of human breast cancer cells

Priority and emerging organic microcontaminants in three Mediterranean river basins: Occurrence, spatial distribution, and identification of river basin specific pollutants

There is a worldwide growing use of chemicals by our developed, industrialized, and technological society. More than 100,000 chemical substances are thus commonly used both by industry and households. Depending on the amount produced, physical-chemical properties, and mode of use, many of them may reach the environment and, notably, the aquatic receiving systems. This may result in undesirable and harmful side-effects on both the human and the ecosystem's health. Mediterranean rivers are largely different from Northern and Central European rivers in terms of hydrological regime, climate conditions (e.g. air temperature, solar irradiation, precipitation), and socio-economics (e.g. land use, tourism, crop types, etc.), with all these factors leading to differences in the relative importance of the environmental stressors, in the classes and levels of the pollutants found and their environmental fate. Furthermore, water scarcity might be critical in affecting water pollution because of the lowered dilution capacity of chemicals. This work provides raw chemical data from different families of microcontaminants identified in three selected Mediterranean rivers (the Sava, Evrotas, and Adige) collected during two sampling campaigns conducted in 2014 and 2015 in three different matrices, namely, water, sediments, and biota (fish). More than 200 organic micropollutants were analyzed, including relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, pesticides, pyrethroid insecticides, flame retardants, and persistent organic pollutants. Data obtained were summarized with some basic statistics for all compound families and matrices analyzed. Observed occurrence and spatial patterns were interpreted both in terms of compound physical-chemical properties and local environmental pressures. Finally, their spatial distribution was examined and their ecotoxicological risk in the water phase was assessed. This allowed locating, at each basin, the most polluted sites (“hot spots”) and identifying the respective river basin specific pollutants (RBSPs), prioritizing them in terms of the potential ecotoxicological risk posed to the aquatic ecosystems.This work has been supported by the European Communities EU 7th Framework Programme Funding under Grant agreement no. 603629-ENV-2013-6.2.1-Globaqua and partly by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-01404) and by the Spanish Ministry of Science, Innovation and Universities (Projects CEX2018-000794-S and IBERAQUA-NET RED2018-102737-T). Special thanks are due to all partners of the GLOBAQUA consortium and the peer review panel for ensuring quality results and a fruitful collaboration within the frame of the project.Peer reviewe