Highlighting Recent Crystalline Engineering Aspects of Luminescent Coordination Polymers Based on F-Elements and Ditopic Aliphatic Ligands.

Three principal factors may influence the final structure of coordination polymers (CPs): (i) the nature of the ligand, (ii) the type and coordination number of the metal center, and (iii) the reaction conditions. Further, flexible carboxylate aliphatic ligands have been widely employed as building blocks for designing and synthesizing CPs, resulting in a diverse array of materials with exciting architectures, porosities, dimensionalities, and topologies as well as an increasing number of properties and applications. These ligands show different structural features, such as torsion angles, carbon backbone number, and coordination modes, which affect the desired products and so enable the generation of polymorphs or crystalline phases. Additionally, due to their large coordination numbers, using 4f and 5f metals as coordination centers combined with aliphatic ligands increases the possibility of obtaining different crystal phases. Additionally, by varying the synthetic conditions, we may control the production of a specific solid phase by understanding the thermodynamic and kinetic factors that influence the self-assembly process. This revision highlights the relationship between the structural variety of CPs based on flexible carboxylate aliphatic ligands and f-elements (lanthanide and actinides) and their outstanding luminescent properties such as solid-state emissions, sensing, and photocatalysis. In this sense, we present a structural analysis of the CPs reported with the oxalate ligand, as the one rigid ligand of the family, and other flexible dicarboxylate linkers with -CH2- spacers. Additionally, the nature of the luminescence properties of the 4f or 5f-CPs is analyzed, and finally, we present a novel set of CPs using a glutarate-derived ligand and samarium, with the formula [2,2'-bipyH][Sm(HFG)2 (2,2'-bipy) (H2O)2]•(2,2'-bipy) (α-Sm) and [2,2'-bipyH][Sm(HFG)2 (2,2'-bipy) (H2O)2] (ß-Sm).

Novel Heterometallic Uranyl-Transition Metal Materials: Structure, Topology, and Solid State Photoluminescence Properties.

Six new uranyl hybrid materials have been synthesized solvothermally utilizing the ligands 2,2'-bipyridine-3,3'-dicarboxylic acid (H2L) and 2,2':6',2''-terpyridine (TPY). The six compounds are classified as either molecular complexes (I0O0 connectivity), [(UO2)(L)(TPY)]·H2O (1), [Ni(TPY)2][(UO2)(L)2]·3H2O (2), and [Cu(TPY)2][(UO2)(L)2]·3H2O (3), or 3D metal-organic frameworks (MOFs, I0O3 connectivity), [Cu2(UO2)2(OH)(C2H3O2)(L)3(TPY)2]·6H2O (4), [Zn2(UO2)2(OH)(NO3)(C2H3O2)(L)3(TPY)2]·4H2O (5), and Na[Ni(UO2)3(OH)(O)(L)3]·9H2O (6). A discussion of the influence of transition metal incorporation, chelating effects of the ligand, and synthesis conditions on the formation of uranyl materials is presented. The structure of compound 6 is of particular note due to large channel-like voids with a diameter of approximately 19.6 Å. A topological analysis of 6 reveals a new topology with a 9-nodal 3,3,3,3,3,3,3,4,5-connected network, designated geg1 hereafter. Further, solid state photoluminescence experiments show emission and lifetimes values consistent with related uranyl compounds.

Luminescent Lanthanide Metal Organic Frameworks as Chemosensing Platforms towards Agrochemicals and Cations.

Since the first studies of luminescent sensors based on metal organic frameworks (MOFs) about ten years ago, there has been an increased interest in the development of specific sensors towards cations, anions, explosives, small molecules, solvents, etc. However, the detection of toxic compounds related to agro-industry and nuclear activity is noticeably scarce or even non-existent. In this work, we report the synthesis and characterization of luminescent lanthanide-based MOFs (Ln-MOFs) with diverse crystalline architectures obtained by solvothermal methods. The luminescent properties of the lanthanides, and the hypersensitive transitions of Eu3+ (5D0→7F2) and Tb3+ (5D4→7F5) intrinsically found in the obtained MOFs in particular, were evaluated and employed as chemical sensors for agrochemical and cationic species. The limit of detection (LOD) of Tb-PSA MOFs (PSA = 2-phenylsuccinate) was 2.9 ppm for [UO22+] and 5.6 ppm for [Cu2+]. The variations of the 4f⁻4f spectral lines and the quenching/enhancement effects of the Ln-MOFs in the presence of the analytes were fully analyzed and discussed in terms of a combinatorial "host⁻guest" vibrational and "in-silico" interaction studies.

Advances in Nanomaterials and Composites Based on Mesoporous Materials as Antimicrobial Agents: Relevant Applications in Human Health.

Nanotechnology has emerged as a cornerstone in contemporary research, marked by the advent of advanced technologies aimed at nanoengineering materials with diverse applications, particularly to address challenges in human health. Among these challenges, antimicrobial resistance (AMR) has risen as a significant and pressing threat to public health, creating obstacles in preventing and treating persistent diseases. Despite efforts in recent decades to combat AMR, global trends indicate an ongoing and concerning increase in AMR. The primary contributors to the escalation of AMR are the misuse and overuse of various antimicrobial agents in healthcare settings. This has led to severe consequences not only in terms of compromised treatment outcomes but also in terms of substantial financial burdens. The economic impact of AMR is reflected in skyrocketing healthcare costs attributed to heightened hospital admissions and increased drug usage. To address this critical issue, it is imperative to implement effective strategies for antimicrobial therapies. This comprehensive review will explore the latest scientific breakthroughs within the metal-organic frameworks and the use of mesoporous metallic oxide derivates as antimicrobial agents. We will explore their biomedical applications in human health, shedding light on promising avenues for combating AMR. Finally, we will conclude the current state of research and offer perspectives on the future development of these nanomaterials in the ongoing battle against AMR.

Sunlight-Driven Photocatalysis for a Set of 3D Metal-Porphyrin Frameworks Based on a Planar Tetracarboxylic Ligand and Lanthanide Ions.

Metal-porphyrin frameworks (MPFs) with trivalent lanthanide ions are the most sought-after materials in the past decade. Their porosities are usually complemented by optical properties imparted by the metal nodes, making them attractive multifunctional materials. Here, we report a novel family of 3D MPFs obtained through solvothermal reactions between tetrakis(4-carboxyphenyl) porphyrin (H4TCPP) and different lanthanide sources, yielding an isostructural family of compounds along the lanthanide series: [Ln2(DMF)(TCPP)1.5] for Ln = La, Ce, Nd, Pr, Er, Y, Tb, Dy, Sm, Eu, Gd, and Tm. Photoluminescent properties of selected phases were explored at room temperature. Also, the photocatalytic performance exhibited by these compounds under sunlight exposure is promising for its implementation in organic pollutant degradation. In order to study the photocatalytic activity of Ln-TCPPs in an aqueous medium, methylene blue (MB) was used as a contaminant model. The efficiency for MB degradation was Sm > Y > Yb > Gd > Er > Eu > either no catalyst or no light, obtaining more than 70% degradation at 120 min with Sm-TCPP. These results open the possibility of using these compounds in optical and optoelectronic devices for water remediation and sensing.

Microfluidic amperometric immunosensor based on porous nanomaterial towards claudin7 determination for colorectal cancer diagnosis.

In this work, we present a microfluidic amperometric immunosensor for cancer biomarker claudin7 (CLD7) determination in circulating extracellular vesicles (EVs) as well as its validation in colorectal cancer (CC) patients. The device is based on synthetized nanosized MIL-125-NH2 particles, covalently anchored to the central channel of the microfluidic immunosensor. This nanomaterial was employed as efficient platform for anti-CLD7 monoclonal antibodies immobilization for specifically recognize and capture CLD7 in EVs samples. Afterwards, the amount of this trapped CLD7 was quantified by HRP-conjugated anti-CLD7-antibody. HRP reacted with its enzymatic substrate in a redox process which resulted in the appearance of a current whose magnitude was directly proportional to the level of CLD7 in the sample. This immunosensor, under optimum conditions, gave the limit of detection for CLD7 of 0.1 pg mL-1, with a wide linear range from 2 to 1000 pg mL-1. The results reported herein open up the use of porous open framework platforms for sensing applications for biomedicine and diagnosis.

A Novel, Quick, and Reliable Smartphone-Based Method for Serum PSA Quantification: Original Design of a Portable Microfluidic Immunosensor-Based System.

We describe a versatile, portable, and simple platform that includes a microfluidic electrochemical immunosensor for prostate-specific antigen (PSA) detection. It is based on the covalent immobilization of the anti-PSA monoclonal antibody on magnetic microbeads retained in the central channel of a microfluidic device. Image flow cytometry and scanning electron microscopy were used to characterize the magnetic microbeads. A direct sandwich immunoassay (with horseradish peroxidase-conjugated PSA antibody) served to quantify the cancer biomarker in serum samples. The enzymatic product was detected at -100 mV by amperometry on sputtered thin-film electrodes. Electrochemical reaction produced a current proportional to the PSA level, with a linear range from 10 pg mL-1 to 1500 pg mL-1. The sensitivity was demonstrated by a detection limit of 2 pg mL-1 and the reproducibility by a coefficient of variation of 6.16%. The clinical performance of this platform was tested in serum samples from patients with prostate cancer (PCa), observing high specificity and full correlation with gold standard determinations. In conclusion, this analytical platform is a promising tool for measuring PSA levels in patients with PCa, offering a high sensitivity and reduced variability. The small platform size and low cost of this quantitative methodology support its suitability for the fast and sensitive analysis of PSA and other circulating biomarkers in patients. Further research is warranted to verify these findings and explore its potential application at all healthcare levels.

Strong photoluminescence and sensing performance of nanosized Ca0.8Ln0.1Na0.1WO4 (Ln = Sm,Eu) compounds obtained by the dry "top-down" grinding method.

Two lanthanide doped nanosystems Ca0.8Ln0.1Na0.1WO4 (Ln = Eu, Sm), denoted as Eu@CWO and Sm@CWO, were prepared by a "top-down" approach in three simple steps: activation, miniaturization by high-energy milling, and further calcination. The solids were thoroughly characterized by X-ray powder diffraction (XRPD) and Scanning-electron microscopy (SEM). Also, analyses of the structure of the compounds and the impact of milling on the crystallite shape and size were carried out through Rietveld refinements. Solid-state photoluminescence was studied in terms of excitation, emission, lifetimes (τobs) and europium-quantum yields. Finally, the Eu@CWO sample was employed as a potential water-stable chemical sensor towards toxic cations, showing a quenching effect in the presence of iron ions.

Tuning the structure, dimensionality and luminescent properties of lanthanide metal-organic frameworks under ancillary ligand influence.

This manuscript addresses the synthesis, structural characterization and optical properties of a 1D coordination polymer (CPs) and 2D and 3D Metal-Organic Frameworks (MOFs) obtained from lanthanide metals, 3-hydroxinaftalene-2,7-disulfonic acid (3-OHNDS) and two different phenanthroline derivates as ancillary ligands. The first is a family of 2D compounds with formula [Ln(3-OHNDS)(H2O)2], where Ln = La(), Pr(), Nd() and Sm(). The addition of 1,10-phenanthroline (phen) in the reaction produces 1D compounds with general formula [Ln(3-OHNDS)(phen)(H2O)]·3H2O, where Ln = La(), Pr(), Nd() and Sm(). Finally, the synthesis with 3,4,7,8-tetramethyl-1,10-phenanthroline (3,4,7,8-TMPhen) as an ancillary ligand results in the formation of the 3D [La(3-OHNDS)(3,4,7,8-TMphen)(H2O)] () compound. The photoluminescence (PL) properties of 1D and 2D compounds were fully investigated in comparison with the 3-OHNDS ligand. One of the most important results was the obtaining of a white-light single-emitter without adding dopant atoms in the structure. With all these results in mind it was possible to establish structure-property relationships.