Recognition and Sensing of Nucleoside Monophosphates by a Dicopper(II) Cryptate

The dicopper complex of a bis-tren cryptand in which the spacer consists of two furane subunits connected in 2,2' by a -CH2- fragment selectively recognizes guanosine monophosphate with respect to other nucleoside monophospates (NMPs) in a MeOH/water solution at pH 7. Recognition is efficiently signaled through the displacement of the indicator 6-carboxyfluorescein bound to the receptor, monitoring its yellow fluorescent emission. Titration experiments evidenced the occurrence of several simultaneous equilibria involving 1:1 and 2:1 receptor/NMP and receptor/indicator complexes. It was demonstrated that the added NMP displaces the indicator from the 2:1 receptor/indicator complex, forming the 1:1 receptor/ analyte inclusion complex. Recognition selectivity is thus ascribed to the nature of nucleotide donor atoms involved in the coordination and their ability to encompass the CuII-CuII distance within the cryptate

Bistren cryptands and cryptates: versatile receptors for anion inclusion and recognition in water

Bistren cryptands can act as selective anion receptors in water in two distinct versions: as hexaprotonated cages and as dicopper(ii) cryptates. Both classes of receptors exert geometrical selectivity, but dimetallic cryptates establish the strongest interactions with the anion

A two-channel Molecular dosimeter for the optical detection of copper(II)

A cyclam-like macrocycle with an integrated push-pull chromophore selectively detects Cu2+ inclusion through both orange-to-yellow colour change and quenching of the green fluorescence

Copper(II) Complexes of Cyclams Containing Nitrophenyl Substituents: Push–Pull Behavior and Scorpionate Coordination of the Nitro Group

The three nitrophenyl–cyclam derivatives (nitrocyclams): 1-(4-nitrophenyl)-1,4,8,11-tetraazacyclotetradecane (2), 1-(2-nitrophenyl)-1,4,8,11-tetraazacyclotetradecane (3), and 1-(2,4-dinitrophenyl)-1,4,8,11-tetraazacyclotetradecane (4), in an MeCN solution, specifically incorporate the CuII ion according to an irreversible process signaled by disappearance of the yellow color for a concentration c < 1 × 10–4 M and by a yellow-to-red color change for c ≥ 1 × 10–3, and must be considered efficient and specific dosimeters of copper(II) salts. When present in the ortho position of the nitrophenyl substituent, the −NO2 group coordinates the CuII according to a scorpionate mode, while the metallocyclam system exhibits a trans-I configuration. In an MeCN solution the red trans-I-[CuII(3)]2+ and trans-I-[CuII(4)]2+ scorpionate complexes slowly convert into the violet trans-III scorpionate complexes. Kinetic aspects of the trans-I-to-trans-III configurational rearrangement were investigated in detail for the [CuII(4)]2+ system. In particular, the conversion is spectacularly accelerated by catalytic amounts of Cl–, NCO–, and F–. While for Cl– and NCO– the effect can be associated with the capability of the anion to stabilize through coordination a possible dissociative intermediate, the amazingly powerful effect of F– must be related to the preliminary deprotonation of one N–H fragment of the macrocycle, driven by the formation of the HF2– ion. Most of the metal complex species studied in solution were isolated in a crystalline form, and their molecular structures were elucidated through X-ray diffraction studies. This study documents the first examples of effective metal coordination by the nitro groupThe financial support of the Italian Ministry of University and Research (PRIN−InfoChem) is gratefully acknowledgedS

Light Emitting Molecular Devices Based on Transition Metals

Multicomponent systems have been designed, which are able to perform defined functions related to light emission and quenching. The desired function can be switched ON/OFF by the operator through a chemical input, either a change of pH or a variation of the redox potential. Transition metals (e.g. Ni(II), Cu(II)) are key constituents within the considered systems, playing a distinctive architectural role and favouring electron transfer processes

Modeling macroalgal forest distribution at Mediterranean scale : present status, drivers of changes and insights for conservation and management

Macroalgal forests are one of the most productive and valuable marine ecosystems, but yet strongly exposed to fragmentation and loss. Detailed large-scale information on their distribution is largely lacking, hindering conservation initiatives. In this study, a systematic effort to combine spatial data on Cystoseira C. Agardh canopies (Fucales, Phaeophyta) was carried out to develop a Habitat Suitability Model (HSM) at Mediterranean scale, providing critical tools to improve site prioritization for their management, restoration and protection. A georeferenced database on the occurrence of 20 Cystoseira species was produced collecting all the available information from published and grey literature, web data portals and co-authors personal data. Data were associated to 55 predictor variable layers in the (ASCII) raster format and were used in order to develop the HSM by means of a Random Forest, a very effective Machine Learning technique. Knowledge about the distribution of Cystoseira canopies was available for about the 14% of the Mediterranean coastline. Absence data were available only for the 2% of the basin. Despite these gaps, our HSM showed high accuracy levels in reproducing Cystoseira distribution so that the first continuous maps of the habitat across the entire basin was produced. Misclassification errors mainly occurred in the eastern and southern part of the basin, where large gaps of knowledge emerged. The most relevant drivers were the geomorphological ones, followed by anthropogenic variables proxies of pollution and urbanization. Our model shows the importance of data sharing to combine a large number of spatial and environmental data, allowing to individuate areas with high probability of Cystoseira occurrence as suitable for its presence. This approach encourages the use of this modeling tool for the prediction of Cystoseira distribution and for supporting and planning conservation and management initiatives. The step forward is to refine the spatial information of presence-absence data about Cystoseira canopies and of environmental predictors in order to address species-specific assessments.peer-reviewe

The challenge of setting restoration targets for macroalgal forests under climate changes

Este artículo contiene 10 páginas, 5 figuras, 1 tabla.The process of site selection and spatial planning has received scarce attention in the scientific literature dealing with marine restoration, suggesting the need to better address how spatial planning tools could guide restoration interventions. In this study, for the first time, the consequences of adopting different restoration targets and criteria on spatial restoration prioritization have been assessed at a regional scale, including the consideration of climate changes. We applied the decision-support tool Marxan, widely used in systematic conservation planning on Mediterranean macroalgal forests. The loss of this habitat has been largely documented, with limited evidences of natural recovery. Spatial priorities were identified under six planning scenarios, considering three main restoration targets to reflect the objectives of the EU Biodiversity Strategy for 2030. Results show that the number of suitable sites for restoration is very limited at basin scale, and targets are only achieved when the recovery of 10% of regressing and extinct macroalgal forests is planned. Increasing targets translates into including unsuitable areas for restoration in Marxan solutions, amplifying the risk of ineffective interventions. Our analysis supports macroalgal forests restoration and provides guiding principles and criteria to strengthen the effectiveness of restoration actions across habitats. The constraints in finding suitable areas for restoration are discussed, and recommendations to guide planning to support future restoration interventions are also included.This study was funded by the EASME–EMFF (Sustainable Blue Economy) Project AFRIMED (http://afrimed-project.eu/, grant agreement N. 789059), supported by the European Community.Peer reviewe

An integrated assessment of the Good Environmental Status of Mediterranean Marine Protected Areas

Este artículo contiene 11 páginas, 2 figuras, 2 tablas.Local, regional and global targets have been set to halt marine biodiversity loss. Europe has set its own policy targets to achieve Good Environmental Status (GES) of marine ecosystems by implementing the Marine Strategy Framework Directive (MSFD) across member states. We combined an extensive dataset across five Mediterranean ecoregions including 26 Marine Protected Areas (MPAs), their reference unprotected areas, and a no-trawl case study. Our aim was to assess if MPAs reach GES, if their effects are local or can be detected at ecoregion level or up to a Mediterranean scale, and which are the ecosystem components driving GES achievement. This was undertaken by using the analytical tool NEAT (Nested Environmental status Assessment Tool), which allows an integrated assessment of the status of marine systems. We adopted an ecosystem approach by integrating data from several ecosystem components: the seagrass Posidonia oceanica, macroalgae, sea urchins and fish. Thresholds to define the GES were set by dedicated workshops and literature review. In the Western Mediterranean, most MPAs are in good/high status, with P. oceanica and fish driving this result within MPAs. However, GES is achieved only at a local level, and the Mediterranean Sea, as a whole, results in a moderate environmental status. Macroalgal forests are overall in bad condition, confirming their status at risk. The results are significantly affected by the assumption that discrete observations over small spatial scales are representative of the total extension investigated. This calls for large-scale, dedicated assessments to realistically detect environmental status changes under different conditions. Understanding MPAs effectiveness in reaching GES is crucial to assess their role as sentinel observatories of marine systems. MPAs and trawling bans can locally contribute to the attainment of GES and to the fulfillment of the MSFD objectives. Building confidence in setting thresholds between GES and non-GES, investing in long-term monitoring, increasing the spatial extent of sampling areas, rethinking and broadening the scope of complementary tools of protection (e.g., Natura 2000 Sites), are indicated as solutions to ameliorate the status of the basin.This article was undertaken within the COST Action 15121 MarCons (http://www.marcons-cost.eu, European Cooperation in Science and Technology), the Interreg MED AMAre Plus (Ref: 8022) and the project PO FEAMP 2014-2020 Innovazione, sviluppo e sostenibilita ` nel settore della pesca e dell’acquacoltura per la Regione Campania (ISSPA 2.51). M.C.U., A.B. have been funded by the project MEDREGION (European Commission DG ENV/MSFD, 2018 call, Grant Agreement 110661/ 2018/794286/SUB/ENV.C2). Aegean Sea data were retrieved from the project PROTOMEDEA (www.protomedea.eu), funded by DG for Marine Affairs and Fisheries of the EC, under Grant Agreement SI2.721917. JB acknowledges support from the Spanish Ministry of Science and Innovation (Juan de la Cierva fellowship FJC 2018-035566-I).With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S).Peer reviewe

The stabilization of high oxidation states of metals through coordination by poly-aza macrocycles

A review with 42 refs. The tendency to stabilize trivalent cations, which is expressed by the value of the M3+/M2p redox potential (M = Cu, Ni, etc.), is regulated by the structural features of the macrocycle (ring size, no. and type of donor N atm.). Axial coordination of the solvent, equatorial interactions, and ligand field contributions are discussed