The plastisphere microbiome in alpine soils alters the microbial genetic potential for plastic degradation and biogeochemical cycling

Plastic is exceedingly abundant in soils, but little is known about its ecological consequences for soil microbiome functioning. Here we report the impacts of polyethylene and biodegradable Ecovio and BI-OPL plastic films buried in alpine soils for 5 months on the genetic potential of the soil microbiome using shotgun metagenomics. The microbiome was more affected by Ecovio and BI-OPL than by polyethylene. Fungi, α- and β-Proteobacteria dominated on the biodegradable films. Ecovio and BI-OPL showed signs of degradation after the incubation, whereas polyethylene did not. Genes involved in cellular processes and signaling (intracellular trafficking, secretion, vesicular transport), as well as metabolism (carbohydrate, lipid and secondary metabolism), were enriched in the plastisphere. Several α/β-hydrolase gene families (cutinase_like, polyesterase-lipase-cutinase, carboxylesterase), which encode enzymes essential to plastic degradation, and carbohydrate-active genes involved in lignin and murein degradation increased on Ecovio and BI-OPL films. Enriched nitrogen fixation and organic N degradation and synthesis genes and decreased nitrification genes on Ecovio altered the biogeochemical cycling, leading to higher ammonium concentrations and depletion of nitrite and nitrate in the soil. Our results indicate that plastics affect the alpine soil microbiome and its functions and suggest that the plastisphere has an untapped microbial potential for plastic biodegradation. + Graphical Abstrac

Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope

[EN] Imines are ubiquitous intermediates in organic synthesis, and the metal-mediated imination of alcohols is one of the most direct and simple methods for their synthesis. However, reported protocols lack compatibility with many other functional groups since basic supports/media, pure oxygen atmospheres, and/or released hydrogen gas are required during reaction. Here we show that, in contrast to previous metal-catalyzed methods, hexa-aqueous Ru(III) catalyzes the imination of primary alcohols with very wide functional group tolerance, at slightly acid pH and under low oxygen atmospheres. The inorganic metal complex can be supported and stabilized, integrally, within either faujasite-type zeolites (Y and X) or a metal organic framework (MOF), to give a reusable heterogeneous catalyst which provides an industrially viable process well below the flammability limit of alcohols and amines.This work was supported by the MINECO (Spain) (Projects CTQ2017-86735-P, CTQ2016-75671-P, CTQ2014-56312-P, CTQ2014-55178-R, and MAT2013-40823-R and Excellence Units "Severo Ochoa" SEV2016-0683 and "Maria de Maeztu" and MDM-2015-0538) and the European Union through ERC-AdG-2014-671093 (SynCatMatch) and the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) (FFABR 2017). M.M. thanks the MINECO for a predoctoral contract. RA. thanks UPV for a postdoctoral contract. J.F.-S. acknowledges financial support from the Subprograma Atraccio de Talent - Contractes Postdoctorals de la Universitat de Valencia. We also acknowledge SOLEIL for provision of the synchrotron radiation facility and thank Pierre Fertey for his assistance.Mon, M.; Adam-Ortiz, R.; Ferrando-Soria, J.; Corma Canós, A.; Pardo, E.; Armentano, D.; Leyva Perez, A. (2018). Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope. ACS Catalysis. 8(11):10401-10406. https://doi.org/10.1021/acscatal.8b03228S104011040681

Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction

[EN] The preparation of novel efficient catalyststhat could be applicable in industrially important chemical processeshas attracted great interest. Small subnanometer metal clusters can exhibit outstanding catalytic capabilities, and thus, research efforts have been devoted, recently, to synthesize novel catalysts bearing such active sites. Here, we report the gram-scale preparation of Ag-2(0) subnanometer clusters within the channels of a highly crystalline three-dimensional anionic metal-organic framework, with the formula [Ag-2(0)]@(Ag2Na2I)-Na-I{Ni-4(II)[Cu-2(II)(Me(3)mpba)(2)](3)}middot48H(2)O [Me(3)mpba(4-) = N,N '-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. The resulting crystalline solid catalystfully characterized with the help of single-crystal X-ray diffractionexhibits high catalytic activity for the catalytic Buchner ring expansion reaction.This work was supported by the Ministero dell'Universita e della Ricerca (Italy), the MICIIN (Spain) (projects PID2020- 115100GB-I00, PID2019-104778GB-I00 and Excellence Unit "Maria de Maeztu" CEX2019-000919-M) , and the Generalitat Valenciana (project PROMETEO/2021/054). Thanks are also extended to the Ramon y Cajal Program (RYC2019-027940-I) (J. F.-S.) and the Diamond Light Source for the awarded beamtime and provision of synchrotron radiation facilities (proposal no. CY22411-1). We particularly acknowledge Dr David Allan and Sarah Barnett for their assistance at the I19 beamline. E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme/ERC grant agreement no 814804, MOF-reactors. M.M. thanks MICIIN from a contract under the Juan de la Cierva program (FJC2019-040523-I). Y.Z. thanks the China Scholarship Council (CSC no: 202009350009) for a Ph.D. fellowship.Tiburcio, E.; Zheng, Y.; Mon-Conejero, M.; Martín, N.; Ferrando-Soria, J.; Armentano, D.; Leyva Perez, A.... (2022). Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction. Inorganic Chemistry. 61:11796-11802. https://doi.org/10.1021/acs.inorgchem.2c0150811796118026

Stable isotope ratio analysis: an emerging tool to trace the origin of falsified medicines

Falsified medicines pose a serious threat to global public health. Over the past few decades, the number of public health issues and seizures of falsified medicines has dramatically increased across the world. The development of new analytical techniques for the identification and traceability of these products hold great promise for innovation to help curtail the high number of deaths caused by the lack of adequate treatments and in combating the criminals responsible for manufacturing these products. This review presents the main approaches, based on stable isotope ratios of the bio-elements, mainly Isotope Ratio Mass Spectrometry and Site-specific Natural Isotopic Fractionation by Nuclear Magnetic Resonance, that can contribute to identifying the origin of these products, both in terms of geographical origin and raw materials employed as well as for the batch controls by the producer

Isolated Fe(III)-O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions

[EN] The search for simple, earth-abundant, cheap, and nontoxic metal catalysts able to perform industrial hydrogenations is a topic of interest, transversal to many catalytic processes. Here, we show that isolated FeIII¿O sites on solids are able to dissociate and chemoselectively transfer H2 to acetylene in an industrial process. For that, a novel, robust, and highly crystalline metal¿organic framework (MOF), embedding FeIII¿OH2 single sites within its pores, was prepared in multigram scale and used as an efficient catalyst for the hydrogenation of 1% acetylene in ethylene streams under front-end conditions. Cutting-edge X-ray crystallography allowed the resolution of the crystal structure and snapshotted the single-atom nature of the catalytic FeIII¿O site. Translation of the active site concept to even more robust and inexpensive titania and zirconia supports enabled the industrially relevant hydrogenation of acetylene with similar activity to the Pd-catalyzed process.This work was supported by the MINECO (Spain) (Projects CTQ2016-75671-P, CTQ2014-56312-P, CTQ2014-55178-R, and Excellence Units "Severo Ochoa" and "Maria de Maeztu" SEV-2016-0683 and MDM-2015-0538) and the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) (FFABR 2017). M.M. thanks the mineco for a predoctoral contract. Thanks are also extended to the Ramon y Cajal Program (E.P.) and the "Suprograma atraccio de talent-contractes postdoctorals de la Universitat de Valencia" (J.F.-S.). A.L.-P. and J.F.S. also thank fBBVA for the concession of a young investigator grants.Tejeda-Serrano, M.; Mon, M.; Ross, B.; Gonell-Gómez, F.; Ferrando-Soria, J.; Corma Canós, A.; Leyva Perez, A.... (2018). Isolated Fe(III)-O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions. Journal of the American Chemical Society. 140(28):8827-8832. https://doi.org/10.1021/jacs.8b04669S882788321402

High-Alpine Permafrost and Active-Layer Soil Microbiomes Differ in Their Response to Elevated Temperatures

The response of microbial communities to the predicted rising temperatures in alpine regions might be an important part of the ability of these ecosystems to deal with climate change. Soil microbial communities might be significantly affected by elevated temperatures, which influence the functioning of soils within high-alpine ecosystems. To evaluate the potential of the permafrost microbiome to adapt to short-term moderate and extreme warming, we set up an incubation experiment with permafrost and active soil layers from northern and southern slopes of a high-alpine mountain ridge on Muot da Barba Peider in the Swiss Alps. Soils were acclimated to increasing temperatures (4–40°C) for 26 days before being exposed to a heat shock treatment of 40°C for 4 days. Alpha-diversity in all soils increased slightly under gradual warming, from 4 to 25°C, but then dropped considerably at 40°C. Similarly, heat shock induced strong changes in microbial community structures and functioning in the active layer of soils from both northern and southern slope aspects. In contrast, permafrost soils showed only minor changes in their microbial community structures and no changes in their functioning, except regarding specific respiration activity. Shifts in microbial community structures with increasing temperature were significantly more pronounced for bacteria than for fungi, regardless of the soil origin, suggesting higher resistance of high-alpine fungi to short-term warming. Firmicutes, mainly represented by Tumebacillus and Alicyclobacillaceae OTUs, increased strongly at 40°C in active layer soils, reaching almost 50% of the total abundance. In contrast, Saccharibacteria decreased significantly with increasing temperature across all soil samples. Overall, our study highlights the divergent responses of fungal and bacterial communities to increased temperature. Fungi were highly resistant to increased temperatures compared to bacteria, and permafrost communities showed surprisingly low response to rising temperature. The unique responses were related to both site aspect and soil origin indicating that distinct differences within high-alpine soils may be driven by substrate limitation and legacy effects of soil temperatures at the field site

H2-fuelled microbial metabolism in Opalinus Clay

In Switzerland, the Opalinus Clay formation is considered the most likely host rock for a deep geological repository for nuclear waste. In deep geological repositories, H2 is expected to be the most abundant gas formed from the degradation of waste and from metal corrosion. The microbial community present in Opalinus Clay is capable of utilizing H2 as an electron donor and sulfate as an electron acceptor to produce hydrogen sulfide. This could be problematic due to its potential for increasing the corrosion of metal waste canisters containing radioactive waste, however, the possible impacts of these processes on the clay rock have not been fully investigated. In this study, a series of microcosm experiments were set-up containing Opalinus Clay and porewater from the Mont Terri underground research laboratory (Switzerland) as an inoculum. Uninoculated microcosms were established to investigate abiotic processes. In the presence of clay, a higher aqueous sulfate concentration was detected than in those with only porewater present and this concentration decreased over time in the inoculated experiments. However, there was no evidence of hydrogen sulfide production in the aqueous phase. In all experiments with clay, there was an increase in aqueous Fe2+ concentrations with the highest concentrations found in uninoculated experiments. The sulfur speciation of the Opalinus Clay was analysed and the results of the inoculated sample suggested that hydrogen sulfide reacted with Fe2+, precipitating iron sulfide minerals. After the incubation period, the microbial community was dominated by the sulfate-reducing Desulfobulbaceae family. The study suggests that H2-fuelled, microbially-mediated sulfate reduction can affect the mineral composition within the Opalinus Clay due to the precipitation of iron sulfide minerals. These precipitation reactions may enhance the long-term integrity of the repository by removing corrosive hydrogen sulfide from solution when sufficient Fe2+ is available and so protecting the canisters containing the nuclear waste

Isotropic soft-core potentials with two characteristic length scales and anomalous behaviour

Isotropic soft-core potentials with two characteristic length scales have been used since 40 years to describe systems with polymorphism. In the recent years intense research is showing that these potentials also display polyamorphism and several anomalies, including structural, diffusion and density anomaly. These anomalies occur in a hierarchy that resembles the anomalies of water. However, the absence of directional bonding in these isotropic potentials makes them different from water. Other systems, such as colloidal suspensions, protein solutions or liquid metals, can be well described by these family of potentials, opening the possibility of studying the mechanism generating the polyamorphism and anomalies in these complex liquids

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single-Molecule Magnets

International audienceWe report the study of a Dy-based metal-organic framework (MOF) with unprecedented magnetic properties. The compound is made of nine-coordinated Dy-III magnetic building blocks (MBBs) with poor intrinsic single-molecule magnet behavior. However, the MOF architecture constrains the MBBs in a one-dimensional structure that induces a ferromagnetic coupling between them. Overall, the material shows a magnetic slow relaxation in absence of external static field and a hysteretic behavior at 0.5K. Low-temperature magnetic studies, diamagnetic doping, and ab initio calculations highlight the crucial role played by the Dy-Dy ferromagnetic interaction. Overall, we report an original magnetic object at the frontier between single-chain magnets and single-molecule magnets that host intrachain couplings that cancel quantum tunneling between the MBBs. This compound is evidence that a bottom-up approach through MOF design can induce spontaneous organization of MBBs able to produce remarkable molecular magnetic materials

Cannabinoid pharmacology in cancer research: A new hope for cancer patients?

Cannabinoids have been used for many centuries to ease pain and in the past decade, the endocannabinoid system has been implicated in a number of pathophysiological conditions, such as mood and anxiety disorders, movement disorders such as Parkinson's and Huntington's disease, neuropathic pain, multiple sclerosis, spinal cord injury, atherosclerosis, myocardial infarction, stroke, hypertension, glaucoma, obesity, and osteoporosis. Several studies have demonstrated that cannabinoids also have anti-cancer activity and as cannabinoids are usually well tolerated and do not produce the typical toxic effects of conventional chemotherapies, there is considerable merit in the development of cannabinoids as potential anticancer therapies. Whilst the presence of psychoactive effects of cannabinoids could prevent any progress in this field, recent studies have shown the value of the non-psychoactive components of cannabinoids in activating apoptotic pathways, inducing anti-proliferative and anti-angiogenic effects. The aforementioned effects are suggested to be through pathways such as ERK, Akt, mitogen-activated protein kinase (MAPK) pathways, phosphoinositide 3-kinase (PI3K) pathways and hypoxia inducible factor 1 (HIF1), all of which are important contributors to the hallmarks of cancer. Many important questions still remain unanswered or are poorly addressed thus necessitating further research at basic pre-clinical and clinical levels. In this review, we address these issues with a view to identifying the key challenges that future research needs to address