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A series of lead(II) complexes incorporating benzoate derivative ligands was prepared: [Pb(2MeOBz)2]n (1), [Pb(2MeOBz)2(H2O)]n (2), [Pb2(1,4Bzdiox)4(DMSO)]n (3), [Pb(1,4Bzdiox)2(H2O)]n (4), [Pb(Pip)2(H2O)]n (5), and [Pb(Ac)(Pip)2(MeOH)]n (6) (2MeOBz: 2-methoxybenzoate; 1,4Bzdiox: 1,4-benzodioxan-5-carboxylate; DMSO: dimethylsulfoxide; Ac: acetate; Pip: piperonylate; MeOH: methanol). All compounds were characterized via elemental analysis, ATR-FTIR spectroscopy, and powder XRD. In addition, the crystal structures of some compounds were elucidated. Compounds 1 and 2, involving 2-methoxybenzoate, were closely related, only differing in the presence of one extra aqua ligand found for the latter. However, this implies key changes in the studied properties, e.g., 2 shows solid-state luminescence that displays a different color as a function of the crystal orientation, while 1 does not. The crystal structure of 2 revealed a 1D coordination polymer. A similar relationship was found between compounds 3 and 4, incorporating 1,4-benzodioxan-5-carboxylate. In this pair, only 4, with aqua ligands, displayed a greenish-yellow-color solid-state luminescence. Furthermore, two new lead(II) piperonylate complexes, 5 and 6, were obtained from the reaction between lead(II) acetate and piperonylic acid. In water, all acetate ligands in the metal precursor were displaced and [Pb(Pip)2(H2O)]n (5) was isolated, while in methanol, a mixed acetate–piperonylate complex, [Pb(Ac)(Pip)2(MeOH)]n (6), was precipitated. Considering only conventional Pb-O bonds, the crystal structure of 6 was described as a 1D coordination polymer, although, additionally, the chains were associated via tetrel bonds, defining an extended 2D architecture.

The development of effective array biosensorsrelies heavily on careful control of the density of surface-immobilized ligands on the transducing platform. In this paperwe describe the synthesis of new dextran−lipase conjugates foruse in immobilizing low molecular weight haptens onto glassplanar waveguides for immunosensor development. Theconjugates were synthesized by immobilizing bacterial thermoalkalophilic lipases (Geobacillus thermocatenulatuslipase 2,BTL2) on agarose macroporous beads, followed by covalent coupling to dextran networks of variable molecular weight (1500−40000). The chimeras were immobilized via nonspecific hydrophobic interactions onto glass planar waveguides modified with1,1,1,3,3,3-hexamethyldisilazane to obtain highly ordered and homogeneous molecular architectures as confirmed by atomic forcemicroscopy. Microcystin LR (MCLR) was covalently bound to the dextran−BTL2 conjugates. The usefulness of this approach inimmunosensor development was demonstrated by determining amounts of MCLR down to a few picograms per liter with anautomated array biosensor and evanescent wave excitation forfluorescence measurements of attached DyLight649-labeledsecondary antibody. Modifying BTL2 with dextrans of an increased molecular weight (>6000) provided surfaces with anincreased loading capacity that was ascribed to the production of three-dimensional surfaces by the effect of analyte binding deepin the volume, leading to expanded dynamic ranges (0.09−136.56 ng L−1), lower limits of detection (0.007±0.001 ng L−1), andlower IC50values (4.4±0.7 ng L−1). These results confirm the effectiveness of our approach for the development of high-performance biosensing platforms., Depto. de Química en Ciencias Farmacéuticas, Fac. de Farmacia, TRUE, pub

The development of nanostructured composites made of metal-organic frameworks (MOFs) and graphene-based components, including exfoliated nanoplates of graphene oxide (GO) or reduced (rGO) graphene oxide, is an area of great interest in gas storage and separation. To improve the industrial viability, it is commonly demanded to build these nanocomposites with the shape of compact units, such as monoliths, foams, pellets, or films. Methods to generate those 3D nanocomposites involving rGO are abundant; however, they become scarce when GO is the desired support due to the difficulty in maintaining the carbon matrix oxidized during the structuration process. In this work, a methodology based on the use of supercritical CO2 (scCO2) is described for the synthesis of nanocomposites involving a discontinuous MOF phase, e.g. nanoparticles (NPs) of HKUST-1, decorating the surface of a continuous GO matrix, with surface oxygen groups favoring MOF attachment. The use of this new supercritical methodology allows the nanostructuration of the composite in the form of 3D aerogels while avoiding the reduction of GO. Enhanced values of textural properties, determined by low-temperature N2 adsorption-desorption, were observed for the nanocomposites in comparison to the values calculated for similar physical mixtures, highlighting an increase of 40-45% in the value of the surface area for samples with a high percentage of HKUST-1. Moreover, the composite aerogels, displaying a type II isotherm, outperform pristine HKUST-1 in regard to the CH4 practical working capacity at high pressure. Particularly, a composite exhibiting more than 2-fold the working capacity of net HKUST-1 NPs was obtained. Columns involving the composite aerogel as the stationary phase were used to study the separation of N2/CO2 and CH4/CO2 gas mixtures. The results showed a high selectivity of the nanostructured HKUST-1@GO composites for CO2, with breakthrough times of ca. 20 min g-1 and stable cyclic operations.

Carbon nanotubes (CNTs), owing to their high surface area-to-volume ratio and hollow core, can be employed as hosts for adsorbed and/or encapsulated molecules. At high temperatures, the ends of CNTs close spontaneously, which is relevant for several applications, including catalysis, gas storage, and biomedical imaging and therapy. This study highlights the influence of the annealing temperature in the range between 400 and 1100 °C on the structure and morphology of single-walled CNTs. The nitrogen adsorption and density functional theory calculations indicate that the fraction of end-closed CNTs increases with temperature. Raman spectroscopy reveals that the thermal treatment does not alter the tubular structure. Insight is also provided into the efficacy of CNTs filling from the molten phase, depending on the annealing temperature. The CNTs are filled with europium (III) chloride and analyzed by using electron microscopy (scanning electron microscopy and high-resolution transmission electron microscopy) and energy-dispersive X-ray spectroscopy, confirming the presence of filling and closed ends. The filling yield increases with temperature, as determined by thermogravimetric analysis. The obtained results show that the apparent surface area of CNTs, fraction of closed ends, and amount of encapsulated payload can be tailored via annealing.

For bone tissue engineering applications, scaffolds that mimic the porous structure of the extracellular matrix are highly desirable. Herein, we employ a PCL/HA-based scaffold with a double-scaled architecture of small pores coupled to larger ones. To improve the osteoinductivity of the scaffold, we incorporate two different growth factors via polydopamine (PDA) coating. As a first step, we identify the maximum amount of PDA that can be deposited onto the scaffold. Next, to allow for the deposition of a second PDA layer which, in turn, will allow to increase the loading of growth factors, we incorporate a dithiol connecting layer. The thiol groups covalently react with the first PDA coating through Michael addition while also allowing for the incorporation of a second PDA layer. We load the first and second PDA layers with bone morphogenic protein-2 (BMP2) and vascular endothelial growth factor (VEGF), respectively, and evaluate the osteogenic potential of the functionalised scaffold by cell viability, alkaline phosphatase activity and the expression of three different osteogenesis-related genes of pre-seeded human mesenchymal stem cells. Through these studies, we demonstrate that the osteogenic activity of the scaffolds loaded with both BMP2 and VEGF is greater than scaffolds loaded only with BMP2. Importantly, the osteoinductivity is higher when the scaffolds are loaded with BMP2 and VEGF in two different PDA layers. Taken together, these results indicate that the as-prepared scaffolds could be a useful construct for bone-tissue applications.

We have previously reported the fabrication of a polycaprolactone and hydroxyapatite composite scaffold incorporating growth factors to be used for bone regeneration. Two growth factors were incorporated employing a multilayered coating based on polydopamine (PDA). In particular, Bone morphogenetic protein-2 (BMP-2) was bound onto the inner PDA layer while vascular endothelial growth factor (VEGF) was immobilized onto the outer one. Herein, the in vitro release of both growth factors is evaluated. A fastest VEGF delivery followed by a slow and more sustained release of BMP-2 was demonstrated, thus fitting the needs for bone tissue engineering applications. Due to the relevance of the crosstalk between bone-promoting and vessel-forming cells during bone healing, the functionalized scaffolds are further assessed on a co-culture setup of human mesenchymal stem cells and human endothelial progenitor cells. Osteogenic and angiogenic gene expression analysis indicates a synergistic effect between the growth factor-loaded scaffolds and the co-culture conditions. Taken together, these results indicate that the developed scaffolds hold great potential as an efficient platform for bone-tissue applications.

The synthesis of 1D cobalt and zinc monometallic and heterometallic coordination polymers (CPs) was carried out applying one-pot synthetic methods by using either supercritical carbon dioxide or ethanol as the solvent. A collection of four 1D CPs were thus obtained by the combination of a metal (or a mixture of metals) with the linker 1,4-bis(4-pyridylmethyl)benzene. The used metallic complexes were zinc and cobalt hexafluoroacetylacetonate, which can easily incorporate pyridine ligands in the coordination sphere of the metal centre. Independently of the used solvent, the precipitated phases involving Zn(II), i.e., homometallic CP of Zn(II) and bimetallic CP of Zn(II)/Co(II), were isostructural. Contrarily, homometallic CPs of Co(II) were precipitated as an isostructural phase of Zn(II) or with a different structure, depending on the used solvent. All the structures were resolved by XRD using synchrotron radiation. In addition, the magnetic properties of the new CPs involving Co(II) were studied. Remarkably, at low temperatures with the application of an external field, they acted as field-induced single molecule magnets.

We present a novel method for processing bacterial cellulose/graphene oxide (BC/GO) aerogels with multifunctional properties. The addition of a small amount of dimethyl sulfoxide (DMSO) to the aqueous dispersion of the nanomaterials during the gelification process affected the water freezing temperature of the system and thereby affecting the porous structure of the aerogel obtained after liophilization. The possibility to obtain small and elongated pore with axial orientation allowed a significant improvement of the structural stability of the aerogels. Moreover, the aerogels reduction by thermal treatment with ammonia gas induced crosslinking between the different nanophases, thus given an incremental factor for the mechanical performance of the aerogels under harsh conditions. The resulting aerogels also showed significant improvements in terms of thermal stability and electrical conductivity. These multifunctional BC/GO aerogels present high potential as sustainable and ecological alternative materials for lightweight packaging, filters for atmosphere and water treatment, or energy applications.