New Promises and Opportunities in 3D Printable Inks Based on Coordination Compounds for the Creation of Objects with Multiple Applications.

This review focuses on the usefulness of coordination bonds to create 3D printable inks and shows how the union of chemistry and 3D technology contributes to new scientific advances, by allowing amorphous or polycrystalline solids to be transformed into objects with the desired shape for successful applications. The review clearly shows how there has been considerable increase in the manufacture of objects based on the combination of organic matrices and coordination compounds. These coordination compounds are usually homogeneously dispersed within the matrix, anchored onto a proper support or coating the printed object, without destroying their unique properties. Advances are so rapid that today it is already possible to 3D print objects made exclusively from coordination compounds without additives. The new printable inks are made mainly with nanoscale nonporous coordination polymers, metal-organic gels, or metal-organic frameworks. The highly dynamic coordination bond allows the creation of objects, which respond to stimuli, that can act as sensors and be used for drug delivery. In addition, the combination of metal-organic frameworks with 3D printing allows the adsorption or selective capacity of the object to be increased, relative to that of the original compound, which is useful in energy storage, gas separation, or water pollutant elimination. Furthermore, the presence of the metal ion can give them new properties, such as luminescence, that are useful for application in sensors or anticounterfeiting. Technological advances, the combination of various printing techniques, and the properties of coordination bonds lead to the creation of surprising, new, printable inks and objects with highly complex shapes that will close the gap between academia and industry for research into coordination compounds.

A Nanostructured Cu(II) Coordination Polymer Based on Alanine as a Trifunctional Mimic Enzyme and Efficient Composite in the Detection of Sphingobacteria.

This research raises the potential use of coordination polymers as new useful materials in two essential research fields, allowing the obtaining of a new multiartificial enzyme with the capacity to inhibit the growth of bacteria resistance. The fine selection of the ligands allows the design of a new 2D coordination polymer (CP), with the formula [Cu2(IBA)2(OH2)4]n·6nH2O, by the combination of Cu (II) as the metal center with a pseudoamino acid (H2IBA = isophthaloyl bis ß-alanine). Quantitative total X-ray fluorescence (TXRF) analyses show that the obtained CP can gradually release Cu (II) ions. Additionally, this CP can be nanoprocessed and transformed into a metal-organic gel (MOG) by using different Cu (II) salt concentrations and the application of ultrasounds. Considering its nanometric dimensions, the slow Cu (II) release and its simple processability, its performance as an artificial enzyme, and its antibacterial ability were explored. The results obtained show the first nanocoordination polymer acting as an artificial multienzyme (peroxidase, catalase, and superoxodismutase) exhibiting antibacterial activity in the presence of hydrogen peroxide, with selective behavior for three bacterium strains (S. spiritovirum, A. faecales, and B. cereus). Indeed, this CP shows a more robust inhibition capacity for Sphingobacterium. Going beyond that, as there are no comfortable and practically clinical tests capable of detecting the presence of Sphingobacteria, the compound can be easily embedded to form moldable gelatin that will facilitate the handling and low-cost commercial kits.

Innovative Microstructural Transformation upon CO2 Supercritical Conditions on Metal-Nucleobase Aerogel and Its Use as Effective Filler for HPLC Biomolecules Separation.

This work contributes to enlightening the opportunities of the anisotropic scheme of non-covalent interactions present in supramolecular materials. It provides a top-down approach based on their selective disruption that herein has been employed to process a conventional microcrystalline material to a nanofibrillar porous material. The developed bulk microcrystalline material contains uracil-1-propionic acid (UPrOH) nucleobase as a molecular recognition capable building block. Its crystal structure consists of discrete [Cu(UPrO)2 (4,4'-bipy)2 (H2 O)] (4,4'-bipy=4,4'-bipyridine) entities held together through a highly anisotropic scheme of non-covalent interactions in which strong hydrogen bonds involving coordinated water molecules provide 1D supramolecular chains interacting between them by weaker interactions. The sonication of this microcrystalline material and heating at 45 °C in acetic acid-methanol allows partial reversible solubilization/recrystallization processes that promote the cross-linking of particles into an interlocked platelet-like micro-particles metal-organic gel, but during CO2 supercritical drying, the microcrystalline particles undergo a complete morphological change towards highly anisotropic nanofibers. This unprecedented top-down microstructural conversion provides a nanofibrillar material bearing the same crystal structure but with a highly increased surface area. Its usefulness has been tested for HPLC separation purposes observing the expected nucleobase complementarity-based separation.

The role of coordination compounds in virus research. Different approaches and trends.

This article aims to provide an overview of the studies focused on using coordination compounds as antiviral agents against different types of viruses. We present various strategies so far used to this end. This article is divided into two sections. The first collects the series of designed antiviral drugs based on coordination compounds. This approach has been developed for many years, starting from the 70s with the discovery of cis-platin (cis-DDP). It has been mainly focused on studying the synergistic effect of a wide variety of new compounds obtained by combining metal ions with organic antiviral ligands. Then, we collect various strategies analyzing the coordination compounds interacting with viruses using different processes such as wrapping viruses, rapid detection of RNA or DNA virus, or nanocarriers. These recent and novel insights help to study viruses from other points of view, allowing to measure their physical and chemical properties. We also highlight a section in which the issue of viruses from a disinfection viewpoint is addressed, using coordination compounds as a tool able to control the release of antiviral and biocide agents. This is an emerging and promising field but this approach is actually little developed. We finally provide a section with a general conclusion and perspectives.

Advances and Novel Perspectives on Colloids, Hydrogels, and Aerogels Based on Coordination Bonds with Biological Interest Ligands.

This perspective article shows new advances in the synthesis of colloids, gels, and aerogels generated by combining metal ions and ligands of biological interest, such as nucleobases, nucleotides, peptides, or amino acids, among other derivatives. The characteristic dynamism of coordination bonds between metal center and biocompatible-type ligands, together with molecular recognition capability of these ligands, are crucial to form colloids and gels. These supramolecular structures are generated by forming weak van der Waals bonds such as hydrogen bonds or π-π stacking between the aromatic rings. Most gels are made up of nano-sized fibrillar networks, although their morphologies can be tuned depending on the synthetic conditions. These new materials respond to different stimuli such as pH, stirring, pressure, temperature, the presence of solvents, among others. For these reasons, they can trap and release molecules or metal ions in a controlled way allowing their application in drug delivery as antimicrobial and self-healable materials or sensors. In addition, the correct selection of the metal ion enables to build catalytic or luminescent metal-organic gels. Even recently, the use of these colloids as 3D-dimensional printable inks has been published. The elimination of the solvent trapped in the gels allows the transformation of these into metal-organic aerogels (MOAs) and metal-organic xerogels (MOXs), increasing the number of possible applications by generating new porous materials and composites useful in adsorption, conversion, and energy storage. The examples shown in this work allow us to visualize the current interest in this new type of material and their perspectives in the short-medium term. Furthermore, these investigations show that there is still a lot of work to be done, opening the door to new and interesting applications.

Multifunctional coordination polymers based on copper with modified nucleobases, easily modulated in size and conductivity.

In this work, three mono- and bidimensional coordination polymers (CPs) based on Cu(II) and Cu(I) ([Cu2(TAcO)2(C2O4)(4,4'-bpy)]·4H2O (CP1), [Cu2(UAcO)2(C2O4)(4,4'-bpy)]·2H2O (CP2) and [Cu2(TAcO)2(4,4'-bpy)] (CP3)), decorated with thymine and uracil-1-acetate (TAcO and UAcO), 4,4'-bipyridine (4,4'-bpy) and oxalate are synthetized. The supramolecular structures of the CPs are based on the formation of non-canonical hydrogen bonds established between the free moieties of nucleobases. Interestingly, the presence of Cu(II) centers provide for compound CP1, magnetism and semiconducting properties. Additionally, CP1 has been doped with iodine, increasing its electrical conductivity up to two orders of magnitude. Moreover, the size of the materials can be modulated from millimeters to the nanoscale, depending on the crystallization conditions and/or using ultrasound.

Facilitating influence of stress on the consolidation of fear memory induced by a weak training: reversal by midazolam pretreatment.

It is well known that an emotionally arousing experience usually results in a robust and persistent memory trace. The present study explored the potential mechanisms involved in the influence of stress on the consolidation of a contextual fear memory in animals subjected to a weak fear training protocol, and whether pretreatment with intra-basolateral amygdala or systemic administration of midazolam (MDZ) prevents the potential stress-induced influence on fear memory formation. A previous restraint session facilitated fear retention, this effect was not due to a sensitized effect of restraint on the footshock experience. MDZ, both systemically or intra-basolateral amygdala infusion prior to the restraint, attenuated the stress-induced promoting influence on fear memory formation. In addition, stress exposure activated the ERK1/2 pathway in basolateral amygdala (BLA) after the weak training procedure but not after the immediate footshock protocol. Similar to our behavioral findings, MDZ attenuated stress-induced elevation of phospho-ERK2 (p-ERK2) in BLA following the acquisition session. Given that the activation of ERK1/2 pathway is essential for associative learning, we propose that stress-induced facilitation of p-ERK2 in BLA is an important mechanism for the promoting influence of stress on the consolidation of contextual fear memory.

ERK activation in the amygdala and hippocampus induced by fear conditioning in ethanol withdrawn rats: modulation by MK-801.

The extracellular signal-regulated kinase (ERK) pathway, which can be activated by NMDA receptor stimulation, is involved in fear conditioning and drug addiction. We have previously shown that withdrawal from chronic ethanol administration facilitated the formation of contextual fear memory. In order to explore the neural substrates and the potential mechanism involved in this effect, we examined: 1) the ERK1/2 activation in the central (CeA) and basolateral (BLA) nuclei of the amygdala and in the dorsal hippocampus (dHip), 2) the effect of the NMDA receptor antagonist MK-801 on fear conditioning and ERK activation and 3) the effect of the infusion of U0126, a MEK inhibitor, into the BLA on fear memory formation in ethanol withdrawn rats. Rats made dependent via an ethanol-containing liquid diet were subjected to contextual fear conditioning on day 3 of ethanol withdrawal. High basal levels of p-ERK were found in CeA and dHip from ethanol withdrawn rats. ERK activation was significantly increased both in control (60min) and ethanol withdrawn rats (30 and 60min) in BLA after fear conditioning. Pre-training administration of MK-801, at a dose that had no effect on control rats, prevented the increase in ERK phosphorylation in BLA and attenuated the freezing response 24h later in ethanol withdrawn rats. Furthermore, the infusion of U0126 into the BLA, but not the CeA, before fear conditioning disrupted fear memory formation. These results suggest that the increased fear memory can be linked to changes in ERK phosphorylation, probably due to NMDA receptor activation in BLA in ethanol withdrawn rats.