A family of Cd(II) coordination polymers constructed from 6-aminopicolinate and bipyridyl co-linkers: study of their growth in paper and photoluminescence sensing of Fe3+ and Zn2+ ions.

In this work, we report on five novel coordination polymers (CPs) based on the linkage of the [Cd(6apic)2] building block [where 6apic = 6-aminopicolinate] by different bipyridine-type organic spacers, forming different coordination compounds with the following formulae: [Cd(µ-6apic)2]n (1), {[Cd(6apic)2(µ-bipy)]·H2O}n (2), {[Cd(6apic)2(µ-bpe)]·2H2O}n (3), [Cd(6apic)(µ-6apic)(µ-bpa)0.5]n (4) and {[Cd2(6apic)4(µ-tmbp)]·7H2O}n (5) [where bipy = 4,4'-bipyridine, bpe = 1,2-di(4-pyridyl)ethylene, bpa = 1,2-di(4-pyridyl)ethane (bpa) and tmbp = 1,3-di(4-pyridyl)propane]. Most of the synthesized compounds form infinite metal-organic rods through the linkage of the building block by the bipyridine-type linker, except in the case of compound 4 whose assembly forms a densely packed 3D architecture. All compounds were fully characterized and their photoluminescence properties were studied experimentally and computationally through density functional theory (DFT) calculations. All compounds display, upon UV excitation, a similar blue emission of variable intensity depending on the linker employed for the connection of the building units, among which compound 2 deserves to be highlighted for its room temperature phosphorescence (RTP) with an emission lifetime of 32 ms that extends to 79 ms at low temperature. These good photoluminescence properties, in addition to its stability in water over a wide pH range (between 2 and 10), motivated us to study compound 2 as a sensor for the detection of metal ions in water, and it showed high sensitivity to Fe3+ through a fluorescence turn-off mechanism and an unspecific turn-on response to Zn2+. Furthermore, the compound is processed as a paper-based analytical device (PAD) in which the phosphorescence emission is preserved, improving the sensing capacity toward Fe3+ ions.

Cerium(III) and 5-methylisophthalate-based MOFs with slow relaxation of magnetization and photoluminescence emission.

Two novel Ce(III) metal organic frameworks (MOFs) with formulas [Ce(5Meip)(H-5Meip)]nGR-MOF-17 and [CeCl(5Meip)(DMF)]nGR-MOF-18 (5Meip = 5-methylisophthalate, DMF = N,N-dimethylformamide) have been synthesized, forming 3-dimensional frameworks. Magnetic measurements show that both compounds present field-induced slow magnetic relaxation under a small applied dc field. For GR-MOF-17, the temperature dependence of relaxation times is best described by a Raman mechanism, whereas for GR-MOF-18, relaxation occurs through a combination of Raman and local-mode pathways. Moreover, when avoiding short Ce⋯Ce interactions by magnetic dilution in GR-MOF-17@La and GR-MOF-18@La, only the local-mode mechanism is responsible for magnetic relaxation. Photophysical studies show the occurrence of ligand-centred luminescence in both compounds and phosphorescence emission at low temperature for GR-MOF-17.

Synthesis, Characterization, and Catalytic Performance of a New Heterobimetallic Y/Tb Metal-Organic Framework with High Catalytic Activity.

A three-dimensional heterobimetallic porous structure with the formula {[Y3.5Tb1.5L6(OH)3(H2O)1.5 (DMF)1.5] n ·1.5H2O·DMF} n (L = 3-amino-4-hydroxybenzoate) (Y/Tb-MOF) has been synthesized and characterized by single crystal and powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), inductively coupled plasma mass spectrometry (ICP-MS), electrophoretic mobility, and Fourier transform infrared (FTIR) spectroscopy. The structure presents two metal environments: a bioaugmented isosceles wedge (mm2) MO8 and a tricapped trigonal prism (-6m2) MN3O6. These configurations facilitate the creation of channels with a diameter of 10.7 Å, enabling its utilization as an active catalyst where the heterobimetallic nature of the assembly will be explored. This mixed-metal metal-organic framework has been tested in the cycloaddition of epoxides with carbon dioxide as well as in the cyanosilylation and hydroboration reactions of carbonylic substrates. Additionally, a monometallic Tb-MOF analogue has been synthesized for comparative evaluation of their catalytic performances. Both the mixed metal and monometallic variants exhibit outstanding activity in the cyanosilylation and hydroboration of carbonyls and in the synthesis of carbonates under CO2 pressure. However, only the latter exhibits high recyclability.

Multifunctional Amino Acid Derivative Coordination Compounds: Novel Contrast Agent and Luminescence Materials.

In this work a family of multidimensional (2-(1H-tetrazol-5-yl)ethyl) amino acid coordination compounds have been synthesized and thoroughly characterized. For this purpose, glycine, valine, phenylalanine and tyrosine have been selected as starting amino acids and Mn2+, Zn2+ and Cd2+ as metallic nodes. From one side, for Mn2+ based dimer magnetic resonance imaging studies have been conducted, prompted by the number and disposition of the coordinated water molecules and taking into consideration the promising future of manganese-based coordination compounds as bio-compatible substitutes to conventional Gd based contrast agents. From another side, d10 block metal-based complexes allowed exploring photoluminescence properties derived by in situ synthesized ligands. Finally, amino acid preserved structural chirality allowed us to examine chiroptical properties, particularly focusing on circularly polarized luminescence.

From field-induced to zero-field SMMs associated with open/closed structures of bis(ZnDy) tetranuclear complexes: a combined magnetic, theoretical and optical study.

We have prepared a bis(compartmental) Mannich base ligand H4L (1,4,8,11-tetraaza-1,4,8,11-tetrakis(2-hydroxy-3-methoxy-5-methylbenzyl)cyclotetradecane) specifically designed to obtain bis(TMIILnIII) tetranuclear complexes (TM = transition metal). In this regard, we have succeeded in obtaining three new complexes of the formula [Zn2(µ-L)(µ-OAc)Dy2(NO3)2]·[Zn2(µ-L)(µ-OAc)Dy2(NO3)(OAc)]·4CHCl3·2MeOH (1) and [TM2(µ-H2L)2(µ-succinate)Ln2(NO3)2] (NO3)2·2H2O·6MeOH (TMII = Zn, LnIII = Dy (2); TMII = Co, LnIII = Dy (3)). Compound 1 contains two different bis(ZnDy) tetranuclear molecules that cocrystallize in the structure, in which acetato bridging ligands connect the ZnII and DyIII ions within each ZnDy subunit. This compound does not exhibit slow magnetic relaxation at zero field, but it is activated in the presence of an applied dc magnetic field and/or by Dy/Y magnetic dilution, showing two relaxation processes corresponding to each of the two different bis(ZnDy) units found in the structure. As revealed by the theoretical calculations, magnetic relaxation in 1 is single-ion in origin and takes place through the first excited state of each DyIII ion. When using the succinato dicarboxylate bridging ligand instead of acetate, compounds 2 and 3 were serendipitously formed, which have a closed structure with the succinate anion bridging two ZnDy subunits belonging to two different ligands. It should be noted that only compound 2 exhibits slow relaxation of magnetization in the absence of an external magnetic field. According to experimental and theoretical data, 2 relaxes through the second excited Kramers doublet (Ueff = 342 K). In contrast, 3 displays field-induced SMM behaviour (Ueff = 203 K). However, the Co/Zn diluted version of this compound 3Zn shows slow relaxation at zero field (Ueff = 347 K). Ab initio theoretical calculations clearly show that the weak ferromagnetic coupling between CoII and DyIII ions is at the origin of the lack of slow relaxation of this compound at zero field. Compound 2 and its diluted analogues 2Y and 3Zn show hysteresis loops at very low temperature, thus confirming their SMM behaviour. Finally, compounds 1 and 2 show DyIII based emission even at room temperature that, in the case of 2, allows us to extract the splitting of the ground 6H15/2 term, which matches reasonably well with theoretical calculations.

Nickel, copper, and zinc dinuclear helicates: how do bulky groups influence their architecture?

The ligand design factors that may influence the isolation of metallosupramolecular helicates or mesocates still deserve to be investigated. In this sense, dinuclear nickel(II), copper(II) and zinc(II) compounds were obtained by electrochemical synthesis using a family of five Schiff base ligands, H2Ln (n = 1-5), derived from bisphenylmethane and functionalized with bulky tert-butyl groups in the periphery and ethyl groups in the spacer. Six of the new complexes were characterized by X-ray crystallography, thus demonstrating that the helicate structure is predominant in the solid state. 1H NMR studies were performed for the zinc complexes to analyze if the helical architecture of the metal complexes is retained in solution. These studies reveal that the presence of a tert-butyl group in the ortho position with respect to the OH group is an essential factor identified for the existence of a helicate conformation in solution.

Spin canting and slow magnetic relaxation in mononuclear cobalt(II) sulfadiazine ternary complexes.

Monomeric [Co(SDZ)2phen] (1) and [Co(SDZ)(bq)Cl] (2) complexes (SDZ = sulfadiazine, phen = 1,10-phenanthroline, and bq = 2,2'-biquinoline) have been synthesized and characterized. X-ray diffraction studies indicate that SDZ acts as a bidentate ligand coordinating through the sulfonamide and the pyrimidine N atoms in both compounds. In complex 1, the coordination sphere consists of two SDZ ligands and a bis-chelating phen ligand, giving rise to a CoN6 coordination sphere. On the other hand, 2 has a CoN4Cl core, with two N-atoms from SDZ and two from the bq ligand. Both compounds have been studied by dc and ac magnetometry and shown to display slow magnetic relaxation under an optimum external dc field (1 kOe) at low temperatures. Moreover, compound 2 displays long range magnetic ordering provided by spin-canted antiferromagnetism, which has been characterized by further field-dependent magnetic susceptibility measurements, FC/ZFC curves, hysteresis loops and frequency-independent ac curves. The signs of the calculated D parameters, positive in 1 and negative in 2, have been rationalized according to the two lowest-lying transitions in the orbital energy diagrams derived from ab initio ligand field theory (AILFT). In a subsequent attempt to reveal the possible hidden zero-field SMM behaviour, Ni(II)-based 3 and Co(II)-doped Ni(II)-based (with a Ni : Co ratio of 0.9 : 0.1) heterometallic compound 2Ni were synthesized.

Zero-Field SMM Behavior Triggered by Magnetic Exchange Interactions and a Collinear Arrangement of Local Anisotropy Axes in a Linear Co3II Complex.

A new linear trinuclear Co(II)3 complex with a formula of [{Co(µ-L)}2Co] has been prepared by self-assembly of Co(II) ions and the N3O3-tripodal Schiff base ligand H3L, which is obtained from the condensation of 1,1,1-tris(aminomethyl)ethane and salicylaldehyde. Single X-ray diffraction shows that this compound is centrosymmetric with triple-phenolate bridging groups connecting neighboring Co(II) ions, leading to a paddle-wheel-like structure with a pseudo-C3 axis lying in the Co-Co-Co direction. The Co(II) ions at both ends of the Co(II)3 molecule exhibit distorted trigonal prismatic CoN3O3 geometry, whereas the Co(II) at the middle presents an elongated trigonal antiprismatic CoO6 geometry. The combined analysis of the magnetic data and theoretical calculations reveal strong easy-axis magnetic anisotropy for both types of Co(II) ions (|D| values higher than 115 cm-1) with the local anisotropic axes lying on the pseudo-C3 axis of the molecule. The magnetic exchange interaction between the middle and ends Co(II) ions, extracted by using either a Hamiltonian accounting for the isotropic magnetic coupling and ZFS or the Lines' model, was found to be medium to strong and antiferromagnetic in nature, whereas the interaction between the external Co(II) ions is weak antiferromagnetic. Interestingly, the compound exhibits slow relaxation of magnetization and open hysteresis at zero field and therefore SMM behavior. The significant magnetic exchange coupling found for [{Co(µ-L)}2Co] is mainly responsible for the quenching of QTM, which combined with the easy-axis local anisotropy of the CoII ions and the collinearity of their local anisotropy axes with the pseudo-C3 axis favors the observation of SMM behavior at zero field.

Faster-acting insulin aspart reduces glycaemic variability in sensor-augmented pump treated type 1 diabetes patients.

AIM: To evaluate the effect of faster aspart over glycaemic variability in type 1 diabetes (T1D) patients treated with sensor-augmented pump (SAP) in a real-world scenario. METHODS: Observational study with SAP-treated adult T1D patients treated with faster aspart for three months. The primary endpoint was the mean amplitude of glucose excursions (MAGE). RESULTS: Fifty patients were treated with faster aspart. Eleven patients (23%) withdrew during the follow-up mainly due to worsening of diabetes control (9 patients). Mean age was 41.2 yrs. (range 21-59) and T1D duration 22.4±10.0 yrs. Mean SAP treatment duration was 3.6±3.1 yrs. We detected a reduction of -7.0 (95% CI -1.1, -12.9; p=0.021) in MAGE at the end of the study. Other glycemic variability indices were also improved: standard deviation of mean interstitial glucose (-3mg/dl; 95% CI, -1, -5; p=0.01), CONGA4 (-2.2; 95% CI -0.3, -4.2; p=0.029), CONGA6 (-2.6; 95% CI -0.6, -4.6; p=0.011), GRADE (-0.5; 95% CI -0.1, -0.9; p=0.022), HBGI (-0.7; 95% CI -0.2, -1.3; p=0.013), J-index (-2.9; 95% CI -0.7, -5.0; p=0.011) and MODD (-5.7; 95% CI -1.7, -9.7; p=0.006). A slight reduction in mean glucose management indicator was also detected (-0.14%; 95% CI, -0.02, -0.27; -1.4mmol/mol; 95% CI -0.1, -3.3; p=0.03). CONCLUSIONS: In SAP-treated T1D patients, faster aspart insulin was associated with reduced glycaemic variability, but also a high percentage of dropouts due to worsened glycaemic control. NCT04233203.

De novo transcriptome sequencing and gene co-expression reveal a genomic basis for drought sensitivity and evidence of a rapid local adaptation on Atlas cedar (Cedrus atlantica).

Introduction: Understanding the adaptive capacity to current climate change of drought-sensitive tree species is mandatory, given their limited prospect of migration and adaptation as long-lived, sessile organisms. Knowledge about the molecular and eco-physiological mechanisms that control drought resilience is thus key, since water shortage appears as one of the main abiotic factors threatening forests ecosystems. However, our current background is scarce, especially in conifers, due to their huge and complex genomes. Methods: Here we investigated the eco-physiological and transcriptomic basis of drought response of the climate change-threatened conifer Cedrus atlantica. We studied C. atlantica seedlings from two locations with contrasting drought conditions to investigate a local adaptation. Seedlings were subjected to experimental drought conditions, and were monitored at immediate (24 hours) and extended (20 days) times. In addition, post-drought recovery was investigated, depicting two contrasting responses in both locations (drought resilient and non-resilient). Single nucleotide polymorphisms (SNPs) were also studied to characterize the genomic basis of drought resilience and investigate a rapid local adaptation of C. atlantica. Results: De novo transcriptome assembly was performed for the first time in this species, providing differences in gene expression between the immediate and extended treatments, as well as among the post-drought recovery phenotypes. Weighted gene co-expression network analysis showed a regulation of stomatal closing and photosynthetic activity during the immediate drought, consistent with an isohydric dynamic. During the extended drought, growth and flavonoid biosynthesis inhibition mechanisms prevailed, probably to increase root-to-shoot ratio and to limit the energy-intensive biosynthesis of secondary metabolites. Drought sensitive individuals failed in metabolism and photosynthesis regulation under drought stress, and in limiting secondary metabolite production. Moreover, genomic differences (SNPs) were found between drought resilient and sensitive seedlings, and between the two studied locations, which were mostly related to transposable elements. Discussion: This work provides novel insights into the transcriptomic basis of drought response of C. atlantica, a set of candidate genes mechanistically involved in its drought sensitivity and evidence of a rapid local adaptation. Our results may help guide conservation programs for this threatened conifer, contribute to advance drought-resilience research and shed light on trees' adaptive potential to current climate change.

Slow Magnetic Relaxation and Modulated Photoluminescent Emission of Coordination Polymer Based on 3-Amino-4-hydroxybenzoate Zn and Co Metal Ions.

As a starting point, a new 3D porous framework with the {[CoL]·0.5DMF·H2O}n chemical formula (where L = 3-amino-4-hydroxybenzoate) is described. Its performance as a single molecule magnet was explored. The study of magnetic properties reveals that Co-MOF shows no frequency-fdependant alternating current (ac) signals under zero direct current (dc) magnetic field, whereas single-molecule magnet behaviour is achieved when CoII ions are diluted in a ZnII based matrix. Interestingly, this strategy renders a bifunctional [CoxZn1-xL]n material that is also characterized by a strong photoluminescent emitting capacity.

Contrasting transcriptomic patterns reveal a genomic basis for drought resilience in the relict fir Abies pinsapo Boiss.

Climate change challenges the adaptive capacity of several forest tree species in the face of increasing drought and rising temperatures. Therefore, understanding the mechanistic connections between genetic diversity and drought resilience is highly valuable for conserving drought-sensitive forests. Nonetheless, the post-drought recovery in trees from a transcriptomic perspective has not yet been studied by comparing contrasting phenotypes. Here, experimental drought treatments, gas-exchange dynamics and transcriptomic analysis (RNA-seq) were performed in the relict and drought-sensitive fir Abies pinsapo Boiss. to identify gene expression differences over immediate (24 h) and extended drought (20 days). Post-drought responses were investigated to define resilient and sensitive phenotypes. Single nucleotide polymorphisms (SNPs) were also studied to characterize the genomic basis of A. pinsapo drought resilience. Weighted gene co-expression network analysis showed an activation of stomatal closing and an inhibition of plant growth-related genes during the immediate drought, consistent with an isohydric dynamic. During the extended drought, transcription factors, as well as cellular damage and homeostasis protection-related genes prevailed. Resilient individuals activate photosynthesis-related genes and inhibit aerial growth-related genes, suggesting a shifting shoot/root biomass allocation to improve water uptake and whole-plant carbon balance. About, 152 fixed SNPs were found between resilient and sensitive seedlings, which were mostly located in RNA-activity-related genes, including epigenetic regulation. Contrasting gene expression and SNPs were found between different post-drought resilience phenotypes for the first time in a forest tree, suggesting a transcriptomic and genomic basis for drought resilience. The obtained drought-related transcriptomic profile and drought-resilience candidate genes may guide conservation programs for this threatened tree species.

Easy Handling and Cost-Efficient Processing of a Tb3+-MOF: The Emissive Capacity of the Membrane-Immobilized Material, Water Vapour Adsorption and Proton Conductivity.

The development of convenient, non-complicated, and cost-efficient processing techniques for packing low-density MOF powders for industry implementation is essential nowadays. To increase MOFs' availability in industrial settings, we propose the synthesis of a novel 3D Tb-MOF (1) and a simple and non-expensive method for its immobilization in the form of pellets and membranes in polymethacrylate (PMMA) and polysulphone (PSF). The photoluminescent properties of the processed materials were investigated. To simulate industrial conditions, stability towards temperature and humidity have been explored in the pelletized material. Water-adsorption studies have been carried out in bulk and processed materials, and because of the considerable capacity to adsorb water, proton-conduction studies have been investigated for 1.

Adsorptive Capacity, Inhibitory Activity and Processing Techniques for a Copper-MOF Based on the 3,4-Dihydroxybenzoate Ligand.

Due to the fast, emerging development of antibiotic-resistant bacteria, the need for novel, efficient routes to battle these pathogens is crucial; in this scenario, metal-organic frameworks (MOFs) are promising materials for combating them effectively. Herein, a novel Cu-MOF-namely 1-that displays the formula [Cu3L2(DMF)2]n (DMF = N,N-dimethylformamide) is described, synthesized by the combination of copper(II) and 3,4-dihydroxybenzoic acid (H3L)-both having well-known antibacterial properties. The resulting three-dimensional structure motivated us to study the antibacterial activity, adsorptive capacity and processability of the MOF in the form of pellets and membranes as a proof-of-concept to evaluate its future application in devices.

Influence of Tartrate Ligand Coordination over Luminescence Properties of Chiral Lanthanide-Based Metal-Organic Frameworks.

The present work reports on a detailed discussion about the synthesis, characterization, and luminescence properties of three pairs of enantiopure 3D metal-organic frameworks (MOFs) with general formula {[Ln2(L/D-tart)3(H2O)2]·3H2O}n (3D_Ln-L/D, where Ln = Sm(III), Eu(III) or Gd(III), and L/D-tart = L- or D-tartrate), and ten pairs of enantiopure 2D coordination polymers (CPs) with general formula [Ln(L/D-Htart)2(OH)(H2O)2]n (2D_Ln-L/D, where Ln = Y(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III) or Yb(III), and L/D-Htart = hydrogen L- or D-tartrate) based on single-crystal X-ray structures. Enantiopure nature of the samples has been further corroborated by Root Mean Square Deviation (RMSD) as well as by circular dichroism (CD) spectra. Solid-state emission spectra of Eu(III), Tb(III), and Dy(III)-based compounds confirm the occurrence of ligand-to-metal charge transfers in view of the characteristic emissions for these lanthanide ions, and emission decay curves were also recorded to estimate the emission lifetimes for the reported compounds. A complete theoretical study was accomplished to better understand the energy transfers occurring in the Eu-based counterparts, which allows for explaining the different performances of 3D-MOFs and 2D-layered compounds. As inferred from the colorimetric diagrams, emission characteristics of Eu-based 2D CPs depend on the temperature, so their luminescent thermometry has been determined on the basis of a ratiometric analysis between the ligand-centered and Eu-centered emission. Finally, a detailed study of the polarized luminescence intensity emitted by the samples is also accomplished to support the occurrence of chiro-optical activity.

Magneto-thermal properties and slow magnetic relaxation in Mn(II)Ln(III) complexes: influence of magnetic coupling on the magneto-caloric effect.

A family of Mn(II)Ln(III) dinuclear and tetranuclear complexes (Ln = Gd and Dy) has been prepared from the compartmental ligands N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromobenzyl)ethylenediamine (H2L1) and N,N',N''-trimethyl-N,N''-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L2). The Mn(II)Gd(III) complexes exhibit antiferromagnetic interactions between Mn(II) and Gd(III) ions in most cases, which are supported by Density Functional Theory (DFT) calculations. Experimental magneto-structural correlations carried out for the reported complexes and other related complexes found in bibliography show that the highest ferromagnetic coupling constants are observed in di-µ-phenoxido bridged complexes, which is due to the planarity of the Mn-(µ-O)2-Gd bridging fragment and to the high Mn-O-Gd angles. The effect of these angles has been studied by DFT calculations performed on a di-µ-phenoxido doubly bridged model. The magneto-thermal properties of the Mn(II)Gd(III) based complexes have also been measured, concluding that the magnitude of the Magneto-Caloric Effect (MCE) is due to the strength rather than to the nature of the magnetic coupling. Moreover, when two Mn(II)Gd(III) dinuclear units are connected by two carbonato-bridging ligands the MCE is enhanced, obtaining a maximum magnetic entropy change of 36.4 Jkg-1 K-1 at ΔB = 7 T and T = 2.2 K. On the other hand, one of the dinuclear Mn(II)Dy(III) complexes displays Single-Molecule Magnet (SMM) behaviour with an energy barrier of 14.8 K under an applied external field of 1000 Oe.

Multifunctional Lanthanide-Based Metal-Organic Frameworks Derived from 3-Amino-4-hydroxybenzoate: Single-Molecule Magnet Behavior, Luminescent Properties for Thermometry, and CO2 Adsorptive Capacity.

Herein, we describe and study a new family of isostructural multifunctional metal-organic frameworks (MOFs) with the formula {[Ln5L6(OH)3(DMF)3]·5H2O}n (where (H2L) is 3-amino-4-hydroxybenzoic acid ligand) for magnetism and photoluminescence. Interestingly, three of the materials (Dy-, Er-, and Yb-based MOFs) present single-molecule magnet (SMM) behavior derived from the magnetic anisotropy of the lanthanide ions as a consequence of the adequate electronic distribution of the coordination environment. Additionally, photoluminescence properties of the ligand in combination with Eu and Tb counterparts were studied, including the heterometallic Eu-Tb mixed MOF that shows potential as ratiometric luminescent thermometers. Finally, the porous nature of the framework allowed showing the CO2 sorption capacity.

Hydrolysis of a carbamate triggered by coordination of metal ions.

The mechanism of carbamate activation promoted by different metal ions has been explored in this work. The reaction of the carbamate ligand H2L with chloride metal salts (M = Ni, Cu, Zn, Cd) leads to the coordination of the metal ions to the ligand, causing hydrolysis of the systems. This self-immolation process results in mononuclear dihydrazone complexes, carbon dioxide and the release of alcohol species from the pendant groups of the carbamate ligand. The conditions under which this process occurs have been studied in detail.

Two Synthetic Approaches to Coinage Metal(I) Mesocates: Electrochemical versus Chemical Synthesis.

We report two different approaches to isolate neutral and cationic mesocate-type metallosupramolecular architectures derived from coinage monovalent ions. For this purpose, we use a thiocarbohydrazone ligand, H2L (1), conveniently tuned with bulky phosphine groups to stabilize the MI ions and prevent ligand crossing to achieve the selective formation of mesocates. The neutral complexes [Cu2(HL)2] (2), [Ag2(HL)2] (3), and [Au2(HL)2] (4) were prepared by an electrochemical method, while the cationic complexes [Cu2(H2L)2](PF6)2 (5), [Cu2(H2L)2](BF4)2 (6), [Ag2(H2L)2](PF6)2 (7), [Ag4(HL)2](NO3)2 (8), and [Au2(H2L)2]Cl2 (9) were obtained by using a metal salt as the precursor. All of the complexes are neutral or cationic dinuclear mesocates, except the silver nitrate derivative, which exhibits a tetranuclear cluster mesocate architecture. The crystal structures of the neutral and cationic copper(I), silver(I), and gold(I) complexes allow us to analyze the influence of synthetic methodology or the counterion role on both the micro- and macrostructures of the mesocates.

Mercury biomagnification in an Antarctic food web of the Antarctic Peninsula.

Under the climate change context, warming Southern Ocean waters may allow mercury (Hg) to become more bioavailable to the Antarctic marine food web (i.e., ice-stored Hg release and higher methylation rates by microorganisms), whose biomagnification processes are poorly documented. Biomagnification of Hg in the food web of the Antarctic Peninsula, one of the world's fastest-warming regions, was examined using carbon (δ13C) and nitrogen (δ15N) stable isotope ratios for estimating feeding habitat and trophic levels, respectively. The stable isotope signatures and total Hg (T-Hg) concentrations were measured in Antarctic krill Euphausia superba and several Antarctic predator species, including seabirds (gentoo penguins Pygoscelis papua, chinstrap penguins Pygoscelis antarcticus, brown skuas Stercorarius antarcticus, kelp gulls Larus dominicanus, southern giant petrels Macronectes giganteus) and marine mammals (southern elephant seals Mirounga leonina). Significant differences in δ13C values among species were noted with a great overlap between seabird species and M. leonina. As expected, significant differences in δ15N values among species were found due to interspecific variations in diet-related to their trophic position within the marine food web. The lowest Hg concentrations were registered in E. superba (0.007 ± 0.008 µg g-1) and the highest values in M. giganteus (12.090 ± 14.177 µg g-1). Additionally, a significant positive relationship was found between Hg concentrations and trophic levels (reflected by δ15N values), biomagnifying nearly 2 times its concentrations at each level. Our results support that trophic interaction is the major pathway for Hg biomagnification in Southern Ocean ecosystems and warn about an increase in the effects of Hg on long-lived (and high trophic level) Antarctic predators under climate change in the future.