Fernando Rojas-González

Crossed and Linked Histories of Tetrapyrrolic Macrocycles and Their Use for Engineering Pores within Sol-Gel Matrices

The crossed and linked histories of tetrapyrrolic macrocycles, interwoven with new research discoveries, suggest that Nature has found in these structures a way to ensure the continuity of life. For diverse applications porphyrins or phthalocyanines must be trapped inside solid networks, but due to their nature, these compounds cannot be introduced by thermal diffusion; the sol-gel method makes possible this insertion through a soft chemical process. The methodologies for trapping or bonding macrocycles inside pristine or organo-modified silica or inside ZrO2 xerogels were developed by using phthalocyanines and porphyrins as molecular probes. The sizes of the pores formed depend on the structure, the cation nature, and the identities and positions of peripheral substituents of the macrocycle. The interactions of the macrocyclic molecule and surface Si-OH groups inhibit the efficient displaying of the macrocycle properties and to avoid this undesirable event, strategies such as situating the macrocycle far from the pore walls or to exchange the Si-OH species by alkyl or aryl groups have been proposed. Spectroscopic properties are better preserved when long unions are established between the macrocycle and the pore walls, or when oligomeric macrocyclic species are trapped inside each pore. When macrocycles are trapped inside organo-modified silica, their properties result similar to those displayed in solution and their intensities depend on the length of the alkyl chain attached to the matrix. These results support the prospect of tuning up the pore size, surface area, and polarity inside the pore cavities in order to prepare efficient catalytic, optical, sensoring, and medical systems. The most important feature is that research would confirm again that tetrapyrrolic macrocycles can help in the development of the authentic pore engineering in materials science.

On Tuning the Fluorescence Emission of Porphyrin Free Bases Bonded to the Pore Walls of Organo-Modified Silica

A sol-gel methodology has been duly developed in order to perform a controlled covalent coupling of tetrapyrrole macrocycles (e.g., porphyrins, phthalocyanines, naphthalocyanines, chlorophyll, etc.) to the pores of metal oxide networks. The resulting absorption and emission spectra intensities in the UV-VIS-NIR range have been found to depend on the polarity existing inside the pores of the network; in turn, this polarization can be tuned through the attachment of organic substituents to the tetrapyrrrole macrocycles before bonding them to the pore network. The paper shows clear evidence of the real possibility of maximizing fluorescence emissions from metal-free bases of substituted tetraphenylporphyrins, especially when these molecules are bonded to the walls of functionalized silica surfaces via the attachment of alkyl or aryl groups arising from the addition of organo-modified alkoxides.

Optimal Surface Amino-Functionalization Following Thermo-Alkaline Treatment of Nanostructured Silica Adsorbents for Enhanced CO2 Adsorption

Special preparation of Santa Barbara Amorphous (SBA)-15, mesoporous silica with highly hexagonal ordered, these materials have been carried out for creating adsorbents exhibiting an enhanced and partially selective adsorption toward CO2. This creation starts from an adequate conditioning of the silica surface, via a thermo-alkaline treatment to increase the population of silanol species on it. CO2 adsorption is only reasonably achieved when the SiO2 surface becomes aminated after put in contact with a solution of an amino alkoxide compound in the right solvent. Unfunctionalized and amine-functionalized substrates were characterized through X-ray diffraction, N2 sorption, Raman spectroscopy, electron microscopy, 29Si solid-state Nuclear Magnetic Resonance (NMR), and NH3 thermal programmed desorption. These analyses proved that the thermo-alkaline procedure desilicates the substrate and eliminates the micropores (without affecting the SBA-15 capillaries), present in the original solid. NMR analysis confirms that the hydroxylated solid anchors more amino functionalizing molecules than the unhydroxylated material. The SBA-15 sample subjected to hydroxylation and amino-functionalization displays a high enthalpy of interaction, a reason why this solid is suitable for a strong deposition of CO2 but with the possibility of observing a low-pressure hysteresis phenomenon. Contrastingly, CH4 adsorption on amino-functionalized, hydroxylated SBA-15 substrates becomes almost five times lower than the CO2 one, thus giving proof of their selectivity toward CO2. Although the amount of retained CO2 is not yet similar to or higher than those determined in other investigations, the methodology herein described is still susceptible to optimization.

Comparative Study of the Optical and Textural Properties of Tetrapyrrole Macrocycles Trapped Within ZrO2, TiO2, and SiO2 Translucent Xerogels

The entrapping of physicochemical active molecules inside mesoporous networks is an appealing field of research due to the myriad of potential applications in optics, photocatalysis, chemical sensing, and medicine. One of the most important reasons for this success is the possibility of optimizing the properties that a free active species displays in solution but now trapped inside a solid substrate. Additionally it is possible to modulate the textural characteristics of substrates, such as pore size, specific surface area, polarity and chemical affinity of the surface, toward the physical or chemical adhesion of a variety of adsorbates. In the present document, two kinds of non-silicon metal alkoxides, Zr and Ti, are employed to prepare xerogels containing entrapped tetrapyrrolic species that could be inserted beforehand in analogue silica systems. The main goal is to develop efficient methods for trapping or binding tetrapyrrole macrocycles inside TiO2 and ZrO2 xerogels, while comparing the properties of these systems against those of the SiO2 analogues. Once the optimal synthesis conditions for obtaining translucent monolithic xerogels of ZrO2 and TiO2 networks were determined, it was confirmed that these substrates allowed the entrapment, in monomeric form, of macrocycles that commonly appear as aggregates within the SiO2 network. From these experiments, it could be determined that the average pore diameters, specific surface areas, and water sorption capacities depicted by each one of these substrates, are a consequence of their own nature combined with the particular structure of the entrapped tetrapyrrole macrocycle. Furthermore, the establishment of covalent bonds between the intruding species and the pore walls leads to the obtainment of very similar pore sizes in the three different metal oxide (Ti, Zr, and Si) substrates as a consequence of the templating effect of the encapsulated species.

Hybrid materials based on functionalised epoxy resin networks

Purpose – The purpose of this paper is to describe how sol‐gel synthesised silica particles are used to modify the characteristics (especially the thermal and mechanical properties) of either an epoxy resin (ER) or a −COOH‐functionalised ER (FER) substrate. In the systems studied here, spherical silica particles are embedded in ER or FER thermosetting polymeric substrates for producing translucent solid materials. There arise covalent unions between the SiO2 silanol surface groups of the particles and the functionalised FER ends, thus rendering SiO2‐FER core‐shell compounds.Design/methodology/approach – The characterisation results confirm the affinity existing between ER and SiO2 particles as well as the existence of chemical bonds at the interface between the silica and FER phases.Findings – An efficient and durable application against corrosion of metallic materials has been developed through the preparation and application of thin surface films made of finely disseminated SiO2 colloidal particles, whi...

A Parallel Simulator for Mercury (Hg) Porosimetry

A parallel simulator, based on the Dual Site-Bond Model of complex media, is developed to study Hg intrusion and extrusion processes in the myriad of voids contained in a porous network. In order to reduce the requirements in RAM and computing resources, the porous network is partitioned into several sub-networks distributed in different cluster processors. The simulator uses shared memory to process (with OpenMP) each sub-network and applies a message passing protocol (with MPI) to allow communication among different processors. We show experimental results that reflect a good performance of our proposal when using different sizes of porous networks in a cluster with 32 nodes, each one having 4 processors.

Skin wound healing with chitosan thin films containing supported silver nanospheres

Dermal wound healing involves complex histo-molecular events aimed to repair the discontinuity of the epithelium. Employing nanometric silver particles provides an efficient antimicrobial effect for several dermal infections. The aim is to elucidate imminent advantages of silver nanoparticles, such as the possibility of modulating the epithelial cell repair process. Through the nanostructural implementation of chitosan thin films supporting silver nanoparticles, it was feasible to evaluate in vivo the efficacy and evolution of dermal recuperation after surgical damage. The characterization of chitosan silver nanoparticle films was performed by UV–visible spectra and Fourier transform infrared spectroscopy, X-ray diffraction, and high-resolution electron microscopy. An important dermal healing was accomplished in animals that were treated with chitosan films supporting silver nanoparticles, as confirmed by a histopathological analysis of the skin after 12 days of treatment. The developed chitosan thin film supporting an optimized amount of silver nanoparticles could be employed to treat diseases related to wound healing.

Pore networks subjected to variable connectivity and geometrical restrictions: A simulation employing a multicore system

Abstract Pore networks considering variable connectivity and geometrical restrictions among voids of assorted sizes are simulated using an 8-multicore computing system. The topology of the resulting networks is visualized in terms of the sizes and connectivity of the pores through color graphics. Results allow the calculation of percolation thresholds, correlation lengths among pores, fractal dimensions of percolation clusters, and conditional probabilities among connected pore sizes. Besides, it is possible to observe disconnected pore islands of different sizes, depending on the structural correlation among pores.

Effects of the Covalent Bonding Entrapment of Tetrapyrrole Macrocycles Inside Translucent Monolithic ZrO2 Xerogels

While searching for adequate sol-gel methodologies for successfully trapping in monomeric and stable form either porphyrins or phthalocyanines, inside translucent monolithic silica xerogels, it was discovered that the interactions of these trapped tetrapyrrole macrocycles with Si-OH surface groups inhibit or spoil the efficient display of physicochemical, especially optical, properties of the confined species. Consequently, we have developed strategies to keep the inserted macrocycle species as far as possible from these interferences by substituting the surface -OH groups for alkyl or aryl groups or trapping these species inside alternative metal oxide networks, such as ZrO2, TiO2, and Al2O3. In the present manuscript, we present, for the first time to our knowledge, a methodology for preserving the spectroscopic characteristics of metal tetrasulfophthalocyanines and cobalt tetraphenylporphyrins trapped inside the pores of ZrO2 xerogels. The results obtained are contrasting with analogous silica systems and demonstrate that, in ZrO2 networks, the macrocyclic species remain trapped in stable and monomeric form while keeping their original spectroscopic characteristics in a better way than when captured inside silica systems. This outcome imply a lower hydrophilic character linked to the existence of a smaller amount of surface hydroxyl groups in ZrO2 networks, if compared to analogous SiO2 xerogel systems. The development and study of the possibility of trapping or fixing synthetic or natural tetrapyrrole macrocycles inside inorganic networks suggest the possibility of synthesizing hybrid solid systems suitable for important applications in technological areas such as optics, catalysis, sensoring and medicine

Anticorrosives, encapsulates, catalytic supports and other novel nanostructured materials

A phenolic-formaldehydic resin (PFR) of the Novolac-type and modified through the attachment of carboxylic end groups (MPR), is used to tailor the morphological and optical properties of sol–gel synthesized silica materials. Silica microparticles are produced from alkoxide precursors in the presence of PFR or MPR resins, leading to a final material consisting of SiO2 globules entangled inside a polymerized resin matrix. Under appropriate experimental conditions, chemical bonds can be established between the SiO2 silanol surface groups and the MPR carboxylic chains, to render SiO2/MPR core-shell-type compounds. The presence of PFR or MPR resins during the sol–gel production of silica microspheres allows to control: (i) the sizes of final SiO2 particles and (ii) the transparency or opacity properties of the final hybrid products. In this way, either opaque or transparent solid substrates can be obtained, depending on the amounts of reactants used to prepare the hybrid specimens. Solid MPR and SiO2/MPR samples were characterized by infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy to determine chemical and textural properties of the hybrid substrates. Under appropriate experimental conditions, chemical bonds could be established between the SiO2 silanol surface groups and the MPR carboxylic chains, to render SiO2/MPR core-shell-type compounds.