Ana M. López-Periago

Preparation of silane-coated TiO2 nanoparticles in supercritical CO2

Nanometric inorganic pigments are widely used as fillers for hybrid composite materials. However, these nanometric powders are hydrophilic in nature and their surface must be functionalized before use. In this work, titanium dioxide (TiO2) nanoparticles were coated using silane coupling agents with alkyl functionality. A supercritical carbon dioxide (scCO2) method was used for surface silanization. Five alkylalkoxysilanes with different alkyl chain length and structure were studied: methyltrimethoxy, isobutyltriethoxy, octyltriethoxy, octyldimethylmethoxy and octadecyltrimethoxysilane. The microstructure and thermal stability of deposited monolayers were characterized using thermogravimetric analysis, ATR-IR spectroscopy, transmission electron microscopy, wettability characterization and low-temperature N2 adsorption/desorption analysis. The use of scCO2 as a solvent provided an effective approach to functionalize individual inorganic nanoparticles due to the enhanced diffusivity of the solution molecules in the aggregates interparticle voids. The trifunctional silanes employed here yielded surfaces with better thermal stabilities and greater hydrophobicities than the used monofunctional silane.

Composite fibrous biomaterials for tissue engineering obtained using a supercritical CO2 antisolvent process

Several techniques have been proposed for producing porous structures or scaffolds for tissue engineering but, as yet, with no optimal solution. With regard to this topic, this paper focuses on the preparation of biocompatible nanometric filler-polymer composites organized in a network of fibers. Titanium dioxide (TiO2) or hydroxyapatite (HAP) nanopowders as the guest particles and poly(lactic acid) (L-PLA) or the blend poly(methylmethacrylate)/poly(epsilon-caprolactone) (PMMA/PCL) as the polymer carrier were selected as model systems for this purpose. A supercritical antisolvent technique was used to produce the composites. In the process developed, the non-soluble particulate filler was suspended in a polymer solution, and both components were sprayed simultaneously into supercritical carbon dioxide (scCO2). Using this technique, polymeric matrices were loaded with approximately 10-20 wt.% of inorganic phase distributed throughout the composite. Two different hybrid materials were prepared: a PMMA/PCL+TiO2 system where either fibers or microparticles were prepared by varying the molecular weight of the used PMMA; and fibers in the case of L-PLA+HAP system. After further post-processing in a three-dimensional network, these nanofibers can potentially be used as scaffolds for tissue engineering.

Towards the synthesis of Schiff base macrocycles under supercritical CO2 conditions

The synthesis of Schiff base macrocycles was achieved using supercritical CO(2) as both solvent and acid catalyst.

Hybrid aerogel preparations as drug delivery matrices for low water-solubility drugs

A comprehensive study of 14 hybrid aerogels of different composition with applications in drug delivery has been carried out. The overall objective was to modulate the release behavior of drug-impregnated aerogels, from an almost instantaneous release to a semi-retarded delivery prolonged during several hours, through internal surface functionalization. The designed hybrid aerogels were composed of silica and gelatin and functionalized with either phenyl, long (16) hydrocarbon chain or methyl moiety. As model systems, three class II active agents (pKa<5.5), ibuprofen, ketoprofen and triflusal, were chosen to impregnate the aerogels. The work relied on the use of supercritical fluid technology for both the synthesis and functionalization of the hybrid aerogels, as well as for the impregnation with an active agent using supercritical CO2 as a solvent. For the impregnated aerogels, in vitro release profiles were recorded under gastric and intestinal pH-conditions using HPLC techniques. The release behavior observed for the three studied drugs was explained considering the measured dissolution profiles of the crystalline drugs, the aerogel composition and its functionalization. Such features are considered of great interest to tailor the bioavailability of drugs with low water solubility.

A clean and effective supercritical carbon dioxide method for the host–guest synthesis and encapsulation of photoactive molecules in nanoporous matrices

The present work is concerned with host–guest processes in the micro- and mesoporous restricted spaces provided by silica aerogels and aluminosilicates. A supercritical carbon dioxide ship-in-a-bottle approach was used for the synthesis of photoactive molecules (triphenylpyrylium and dimethoxyltrityl cations) inside these nanoporous matrices. The resulting hybrid nanocomposites can act as stable and recoverable heterogeneous photocatalysts, having obvious advantages with respect to the more easily degraded organic cations frequently used in homogeneous catalysis. Two aspects of green chemistry are combined in this study to produce nanoporous materials loaded with cationic photosensitizers: (i) the use of supercritical carbon dioxide as a reaction medium in one-pot and as a zero waste technology, and (ii) the use of transparent high surface area nanoporous supports that are expected to be more effective for the target photoactive applications than traditional opaque microporous matrices.

Hybrid aminopolymer–silica materials for efficient CO2 adsorption

The present work focuses on the development of a new eco-efficient chemical method for the polymerization of aziridine to hyperbranched polyethyleneimine (PEI) into mesoporous silica by using compressed CO2 as a solvent, reaction medium and catalyst. PEI was in situ grafted into MCM-41 and silica gel substrates, with pore diameters of 3.8 and 9.0 nm, respectively. The optimal polymerization conditions were found by varying the reaction pressure (1.0–10 MPa), temperature (25–45 °C) and time (20–400 min). The thermal stability analysis indicated that aminopolymer chains were covalently attached on the amorphous silica surface. The described compressed CO2 route for the synthesis of high amine content hybrid products (6–8 mmolN g−1) is a very fast method, with processing times in the order of few minutes even at very low working pressures (1.0 MPa), being a step forward in the design of efficient hybrid aminopolymer nanocomposites for CO2 capture. The adsorptive behavior of the prepared hybrid materials was experimentally established by recording the N2 (−196 °C) and CO2 (25, 50 and 75 °C) adsorption isotherms. Results were compared to molecular simulation studies performed using Grand Canonical Monte Carlo for either N2 or CO2 adsorbed on amino modified MCM-41, thus helping to elucidate the predominant PEI configuration present in the functionalized materials.

Bottom-up approach for the preparation of hybrid nanosheets based on coordination polymers made of metal–diethyloxaloacetate complexes linked by 4,4′-bipyridine

In this work, three synthetic approaches were examined to obtain one dimensional (1D) coordination polymers with the formula [M(deox)2(bpy)]∞ (M = Co, Cu, Mn, Ni, Zn) (deox = diethyl oxaloacetate; bpy = 4,4′-bipyridine). These compounds precipitated as nanosheets arranged in different morphologies as a function of the medium used for the synthesis. Precursor [M(deox)2(H2O)x] (x = 1 for Cu, x = 2 for the other metals) molecular complexes were characterized by powder XRD. Besides, the 1H-NMR spectrum of the diamagnetic Zn(II) complex was measured, and the crystal structure of the Cu complex was elucidated to clarify the coordination mode of the deox ligand. These molecular complexes were used as the building blocks to prepare 1D coordination polymers, using 4,4-bipyridine as the organic linker. The first crystallization strategy involved the reaction between [M(deox)2(H2O)x] and bpy in methanol or ethanol. The second approach involved the use of the same reactants in supercritical CO2 (scCO2) and ethanol as a co-solvent (2% v/v). The third route required the previous preparation of [M(deox)2(tbpy)2]·nH2O adducts (tbpy = 4-tert-butylpyridine; n = 1 for Co, n = 2 for Cu and Zn, n = 1.5 for Mn and x = 0 for Ni) as scCO2 soluble precursors. The high solubility of these derivatives allowed the synthesis of the target coordination polymers in pure scCO2, i.e. avoiding the use of a co-solvent. All of the samples obtained from each strategy had a laminar morphology with nanometric thickness. The samples prepared using scCO2, independently of the use or not of a co-solvent, showed the formation of 15–60 nm thick flakes arranged in a desert rose type conformation. Those obtained using conventional liquid solvents had multiple, closely packed sheets of 40–80 nm thickness, with lateral dimensions in the order of tens of micrometers.

An Unprecedented Stimuli‐Controlled Single‐Crystal Reversible Phase Transition of a Metal–Organic Framework and Its Application to a Novel Method of Guest Encapsulation

The flexibility and unexpected dynamic behavior of a third-generation metal-organic framework are described for the first time. The synthetic strategy is based on the flexibility and spherical shape of dipyridyl-based carborane linkers that act as pillars between rigid Co/BTB (BTB: 1,3,5-benzenetricarboxylate) layers, providing a 3D porous structure (1). A phase transition of the solid can be induced to generate a new, nonporous 2D structure (2) without any loss of the carborane linkers. The structural transformation is visualized by snapshots of the multistep single-crystal-to-single-crystal transformation by single-crystal and powder X-ray diffraction. Poor hydrogen bond acceptors such as MeOH, CHCl3 or supercritical CO2 induce such a 3D to 2D transformation. Remarkably, the transformation is reversible and the 2D phase 2 is further converted back into 1 by heating in dimethylformamide. The energy requirements involved in such processes are investigated using periodic density functional theory calculations. As a proof of concept for potential applications, encapsulation of C60 is achieved by trapping this molecule during the reversible 2D to 3D phase transition, whereas no adsorption is observed by straight solvent diffusion into the pores of the 3D phase.

Preparation and Characterization of Graphene Oxide Aerogels: Exploring the Limits of Supercritical CO2 Fabrication Methods

The supercritical carbon dioxide (scCO2 ) synthesis of non-reduced graphene oxide (GO) aerogels from dispersions of GO in ethanol is here reported as a low-cost, efficient, and environmentally friendly process. The preparation is carried out under the mild conditions of 333 K and 20 MPa. The high aspect ratio of the used GO sheets (ca. 30 μm lateral dimensions) allowed the preparation of aerogel monoliths by simultaneous scCO2 gelation and drying. Solid-state characterization results indicate that a thermally-stable mesoporous non-reduced GO aerogel was obtained by using the supercritical procedure, keeping most of the surface oxygenated groups on the GO sheets, thus, facilitating further functionalization. Moreover, the monoliths have a very low density, high specific surface area, and excellent mechanical integrity; characteristics which rival those of most light-weight reduced graphene aerogels reported in the literature.