Mercury clathration-driven phase transition in a luminescent bipyrazolate metal-organic framework: a multitechnique investigation

Mercury is one of the most toxic heavy metals. By virtue of its triple bond, the novel ligand 1,2-bis(1H-pyrazol-4-yl)ethyne (H2BPE) was expressly designed and synthesized to devise metal-organic frameworks (MOFs) exhibiting high chemical affinity for mercury. Two MOFs, Zn(BPE) and Zn(BPE)·nDMF [interpenetrated i-Zn and noninterpenetrated ni-Zn·S, respectively; DMF = dimethylformamide], were isolated as microcrystalline powders. While i-Zn is stable in water for at least 15 days, its suspension in HgCl2 aqueous solutions prompts its conversion into HgCl2@ni-Zn. A multitechnique approach allowed us to shed light onto the observed HgCl2-triggered i-Zn-to-HgCl2@ni-Zn transformation at the molecular level. Density functional theory calculations on model systems suggested that HgCl2 interacts via the mercury atom with the carbon-carbon triple bond exclusively in ni-Zn. Powder X-ray diffraction enabled us to quantify the extent of the i-Zn-to-HgCl2@ni-Zn transition in 100-5000 ppm HgCl2 (aq) solutions, while X-ray fluorescence and inductively coupled plasma-mass spectrometry allowed us to demonstrate that HgCl2 is quantitatively sequestered from the aqueous phase. Irradiating at 365 nm, an intense fluorescence is observed at 470 nm for ni-Zn·S, which is partially quenched for i-Zn. This spectral benchmark was exploited to monitor in real time the i-Zn-to-HgCl2@ni-Zn conversion kinetics at different HgCl2 (aq) concentrations. A sizeable fluorescence increase was observed, within a 1 h time lapse, even at a concentration of 5 ppb. Overall, this comprehensive investigation unraveled an intriguing molecular mechanism, featuring the disaggregation of a water-stable MOF in the presence of HgCl2 and the self-assembly of a different crystalline phase around the pollutant, which is sequestered and simultaneously quantified by means of a luminescence change. Such a case study might open the way to new-conception strategies to achieve real-time sensing of mercury-containing pollutants in wastewaters and, eventually, pursue their straightforward and cost-effective purification

Chemical Composition, Antioxidant, Antimicrobial and Antidiabetic Potential of Philodendron Bipinnatifidum Schott ex Endl

Many of the species used in popular medicine do not have their biological activities already proven by scientific studies. Among these species, the endemic South American Philodendron bipinnatifidum Schott ex Endl deserves special attention since it is already in use in popular medicine for inflammation cases, such as erysipelas, orchitis and ulcers. This study evaluated the antioxidant, antimicrobial and antidiabetic activities of extracts of the hastes de P. bipinnatifidum. The ethanolic extract showed a significant antioxidant potential. The ethyl acetate extract resulted in high antimicrobial activity against Streptococcus pyogenes. The most significant biological activity of ethyl acetate extract relates to its chemical composition when compared with ethanolic extract, which showed the highest concentration of bioactive compounds. In vitro antidiabetic activity was only evaluated for ethyl acetate extract, resulting in inhibition of intestinal disaccharidases (maltase and sucrase) at concentration of 500 μg/mL

Quantifying spatial variation in the uptake of microplastic by mussels using biodeposit traps: A field-based study

Spatial uptake patterns of microplastics (MP) by marine species are largely unexplored under field conditions. A novel “biodeposit trap” that measure uptake and egestion of MP by suspension-feeders through the analysis of their biodeposits, was designed and used to estimate the spatial variation of these processes by mussels in field conditions. Traps containing wild or farmed mussels or control empty shells were deployed at three sites characterised by different MP concentrations and water flow conditions. A different MP dimensional composition was observed between MP pools present in biodeposit and control traps, with the latter shifted towards higher dimensional range (0.05–5 mm). Conversely, mussels accumulated small MP (0.02–0.05 mm) into their biodeposits without any significant difference between wild and farmed specimens. MP uptake rates were on average 4–5 times higher at the site where MP contamination was expected to be highest and where water flow conditions were considered moderate