Rhodium and copper 6-methylpicolinate complexes. Structural diversity and supramolecular interaction study

Seven new coordination compounds with 6-methylpicolinic acid (6-HMepic) and rhodium(III) or copper(II) of formula [Rh(6-Mepic)3] (1), [Rh(6-Mepic)2(H2O)Cl] (2), [Rh(6-HMepic)(6-Mepic)Cl2]·3.5(H2O) (3), [Cu(6-Mepic)2(H2O)]·H2O (4), [Cu(6-Mepic)2]n, (5), [Cu(6-Mepic)(6-HMepic)I] (6) and [Cu(6-Mepic)(6-HMepic)Cl] (7) have been obtained. Their syntheses have been rationalized, and their structural and supramolecular characteristics have been studied and compared with other similar rhodium and copper picolinate complexes previously reported, in order to stablish structural correlations and analogies. The electrical properties of coordination polymer [Cu(6-Mepic)2]n (5) have been also analyzed and it has been found that it shows a moderated electrical transport along the chain.We thank the financial support from the Spanish Ministerio de Economía y Competitividad (MAT2013-46502-C2-2P and MAT2013-46753-C2-1P). Also the scientific computing center (CCC) of the Autonoma University of Madrid for their tim

1,3-Propanediol production from glycerol with a novel biocatalyst Shimwellia blattae ATCC 33430: Operational conditions and kinetics in batch cultivations

Shimwellia blattae ATCC 33430 as biocatalyst in the conversion of 1,3-propanediol from glycerol is herein evaluated. Several operational conditions in batch cultivations, employing pure and raw glycerol as sole carbon source, were studied. Temperature was studied at shaken bottle scale, while pH control strategy, together with the influence of raw glycerol and its impurities during fermentation were studied employing a 2 L STBR. Thereafter, fluid dynamic conditions were considered by changing the stirring speed and the gas supply (air or nitrogen) in the same scale-up experiments. The best results were obtained at a termperature of 37ºC, an agitation rate of 200 rpm, with free pH evolution from 6.9 and subsequent control at 6.5 and no gas supply during the fermentation, employing an initial concentration of 30 g/L of raw glycerol. Under these conditions, the biocatalyst is competitive, leading to results in line with other previous works in the literature in batch conditions, reaching a final concentration of 1,3-propanediol of 13.84 g/L, with a yield of 0.45 g/g and a productivity of 1.19 g/(L·h) from raw glycerol

Additional binding sites for anionic phospholipids and calcium ions in the crystal structures of complexes of the C2 domain of protein kinase Cα

The C2 domain of protein kinase Cα (PKCα) corresponds to the regulatory sequence motif, found in a large variety of membrane trafficking and signal transduction proteins, that mediates the recruitment of proteins by phospholipid membranes. In the PKCα isoenzyme, the Ca2+-dependent binding to membranes is highly specific to 1,2-sn-phosphatidyl-L-serine. Intrinsic Ca2+ binding tends to be of low affinity and non-cooperative, while phospholipid membranes enhance the overall affinity of Ca2+ and convert it into cooperative binding. The crystal structure of a ternary complex of the PKCα-C2 domain showed the binding of two calcium ions and of one 1,2-dicaproyl-sn-phosphatidyl-L-serine (DCPS) molecule that was coordinated directly to one of the calcium ions. The structures of the C2 domain of PKCα crystallised in the presence of Ca2+ with either 1,2-diacetyl-sn-phosphatidyl-L-serine (DAPS) or 1,2-dicaproyl-sn-phosphatidic acid (DCPA) have now been determined and refined at 1.9 Å and at 2.0 Å, respectively. DAPS, a phospholipid with short hydrocarbon chains, was expected to facilitate the accommodation of the phospholipid ligand inside the Ca2+-binding pocket. DCPA, with a phosphatidic acid (PA) head group, was used to investigate the preference for phospholipids with phosphatidyl-L-serine (PS) head groups. The two structures determined show the presence of an additional binding site for anionic phospholipids in the vicinity of the conserved lysine-rich cluster. Site-directed mutagenesis, on the lysine residues from this cluster that interact directly with the phospholipid, revealed a substantial decrease in C2 domain binding to vesicles when concentrations of either PS or PA were increased in the absence of Ca2+. In the complex of the C2 domain with DAPS a third Ca2+, which binds an extra phosphate group, was identified in the calcium-binding regions (CBRs). The interplay between calcium ions and phosphate groups or phospholipid molecules in the C2 domain of PKCα is supported by the specificity and spatial organisation of the binding sites in the domain and by the variable occupancies of ligands found in the different crystal structures. Implications for PKCα activity of these structural results, in particular at the level of the binding affinity of the C2 domain to membranes, are discussed. © 2002 Elsevier Science Ltd. All rights reserved.This research was supported by grants PB98-0389 to the Universidad de Murcia, and BIO099-0865 to the IBMB and by 1FD97-1558 from DGESIC (Spain) to a collaborative project between the Universidad de Murcia and the IBMB. Data were collected at the EMBL protein crystallography beamlines at ESRF (Grenoble) within a Block Allocation Group (BAG Barcelona), as at ESRF BM14. This work was supported financially by the ESRF and by grant HPRI-CT-1999-00022 of the European Union.Peer Reviewe

Wildlife and Antibiotic Resistance

Antibiotic resistance is a major human health problem. While health care facilities are main contributors to the emergence, evolution and spread of antibiotic resistance, other ecosystems are involved in such dissemination. Wastewater, farm animals and pets have been considered important contributors to the development of antibiotic resistance. Herein, we review the impact of wildlife in such problem. Current evidence supports that the presence of antibiotic resistance genes and/or antibiotic resistant bacteria in wild animals is a sign of anthropic pollution more than of selection of resistance. However, once antibiotic resistance is present in the wild, wildlife can contribute to its transmission across different ecosystems. Further, the finding that antibiotic resistance genes, currently causing problems at hospitals, might spread through horizontal gene transfer among the bacteria present in the microbiomes of ubiquitous animals as cockroaches, fleas or rats, supports the possibility that these organisms might be bioreactors for the horizontal transfer of antibiotic resistance genes among human pathogens. The contribution of wildlife in the spread of antibiotic resistance among different hosts and ecosystems occurs at two levels. Firstly, in the case of non-migrating animals, the transfer will take place locally; a One Health problem. Paradigmatic examples are the above mentioned animals that cohabit with humans and can be reservoirs and vehicles for antibiotic resistance dissemination. Secondly, migrating animals, such as gulls, fishes or turtles may participate in the dissemination of antibiotic resistance across different geographic areas, even between different continents, which constitutes a Global Health issue. Copyright © 2022 Laborda, Sanz-García, Ochoa-Sánchez, Gil-Gil, Hernando-Amado and Martínez

Metamorphic Ga0.76In0.24As/GaAs0.75Sb0.25 tunnel junctions grown on GaAs substrates

Lattice-matched and pseudomorphic tunnel junctions have been developed in the past for application in a variety of semiconductor devices, including heterojunction bipolar transistors, vertical cavity surface-emitting lasers, and multijunction solar cells. However, metamorphic tunnel junctions have received little attention. In 4-junction Ga0.51In0.49P/GaAs/Ga0.76In0.24As/Ga0.47In0.53As inverted-metamorphic solar cells (4J-IMM), a metamorphic tunnel junction is required to series connect the 3rd and 4th junctions. We present a tunnel junction based on a metamorphic Ga0.76In0.24As/GaAs0.75Sb0.25 structure for this purpose. This tunnel junction is grown on a metamorphic Ga0.76In0.24As template on a GaAs substrate. The band offsets in the resulting type-II heterojunction are calculated using the first-principles density functional method to estimate the tunneling barrier height and assess the performance of this tunnel junction against other material systems and compositions. The effect of the metamorphic growth on the performance of the tunnel junctions is analyzed using a set of metamorphic templates with varied surface roughness and threading dislocation density. Although the metamorphic template does influence the tunnel junction performance, all tunnel junctions measured have a peak current density over 200 A/cm2. The tunnel junction on the best template has a peak current density over 1500 A/cm2 and a voltage drop at 15 A/cm2 (corresponding to operation at 1000 suns) lower than 10 mV, which results in a nearly lossless series connection of the 4th junction in the 4J-IMM structure.The authors thankfully acknowledge the invaluable support by W. Olavarria and M. Young growing and processing the semiconductor devices. I. Garcıa holds an IOF grant from the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme (FP7/ 2007-2013) under REA grant agreement No. 299878. This work is supported by the U.S. Department of Energy under Contract No. DE-AC36-08-GO28308 with the National Renewable Energy Laboratory

Reversible stimulus-responsive Cu(i) iodide pyridine coordination polymer

We present a structurally flexible copper–iodide–pyridine-based coordination polymer showing drastic variations in its electrical conductivity driven by temperature and sorption of acetic acid molecules. The dramatic effect on the electrical conductivity enables the fabrication of a simple and robust device for gas detection. X-ray diffraction studies and DFT calculations allow the rationalisation of these observations.We are thankful for support from MICINN (MAT2013-46753-C2-1-P, MAT2013-46502-C2-1/2-P and CTQ2011-26507), Eusko Jaurlaritza (S-PE13UN016) and Generalitat Valenciana PrometeoII/2014/076

Interrelationship between phase transition characteristics and piezoelectric response in lead lanthanum zirconate titanate relaxor ceramics

Dielectric and piezoelectric responses are investigated in relaxor-like lanthanum-modified lead zirconate titanate (PLZT) ceramics, for a La/Zr/Ti ratio of x/60/40 (x = 8 and 10 at.%), obtained by the conventional ceramic method. No significant differences were observed from the room temperature ferroelectric properties, for both PLZT compositions. On the other hand, from evaluation of the nonlinear dielectric response in terms of the Rayleigh’s model, a typical ‘soft’ behaviour is achieved in both materials, although the increments of the dielectric losses are slightly higher than the predicted by this model. The piezoelectric coefficient shows a remarkable increment with the applied dynamics stress, nevertheless without noticeable differences as a function of the lanthanum concentration. However, a significant difference is displayed in the weak-field direct longitudinal piezoelectric response. The dielectric properties revealed a higher diffuseness degree of the phase transition for the highest lanthanum content composition (PLZT 10/60/40). Thus, the observed difference in the piezoelectric response is discussed based on the nature of the phase transition in the studied relaxor materials.Postprint (published version

Zone design of specific sizes using adaptive additively weighted voronoi diagrams

Territory or zone design processes entail partitioning a geographic space, organized as a set of areal units, into different regions or zones according to a specific set of criteria that are dependent on the application context. In most cases, the aim is to create zones of approximately equal sizes (zones with equal numbers of inhabitants, same average sales, etc.). However, some of the new applications that have emerged, particularly in the context of sustainable development policies, are aimed at defining zones of a predetermined, though not necessarily similar, size. In addition, the zones should be built around a given set of seeds. This type of partitioning has not been sufficiently researched; therefore, there are no known approaches for automated zone delimitation. This study proposes a new method based on a discrete version of the adaptive additively weighted Voronoi diagram that makes it possible to partition a two-dimensional space into zones of specific sizes, taking both the position and the weight of each seed into account. The method consists of repeatedly solving a traditional additively weighted Voronoi diagram, so that each seed?s weight is updated at every iteration. The zones are geographically connected using a metric based on the shortest path. Tests conducted on the extensive farming system of three municipalities in Castile-La Mancha (Spain) have established that the proposed heuristic procedure is valid for solving this type of partitioning problem. Nevertheless, these tests confirmed that the given seed position determines the spatial configuration the method must solve and this may have a great impact on the resulting partition