Open Access
Bioavailability of heavy metals in soils amended with sewage sludge
(Agricultural Institute of Canada, 2002) Morera Luzán, María Teresa; Echeverría Morrás, Jesús; Garrido Segovia, Julián José; Química Aplicada; Kimika Aplikatua
The recycling of sewage sludge to agricultural land results in the slow accumulation of potentially toxic heavy metals in soils. A greenhouse experiment was conducted to determine the bioavailability of Cu, Ni, Pb and Zn applied to soils in urban anaerobically stabilized sewage sludge. The soils were Lithic Haplumbrept (Lh), Calcixerollic Xerochrept (Cx1 and Cx2) and Paralithic Xerorthent (Px). Sunflower plants (Helianthus annuus L) were grown in. the soils following amendment with the sludge. The addition of sewage sludge markedly increased the average dry weight of the plants in the soils that had lower yields without sludge addition (Lh, Cx2, and Px). The acid pH of the Lh soil favoured the bioavailability of Zn from sewage sludge. The bioavailability of Cu was greater in the alkaline soils than in the acidic soil (Lh), which can be attributed to the high organic matter content of the Lh soil which complexes Cu and impairs its uptake by the plants. The concentration of metals in the plants increased with the sewage sludge dose. The effect of the soil type on the metal concentration in plants was greater that the effect of the dose.
Open Access
Phenyl siloxane hybrid xerogels: structure and porous texture
(Springer US, 2019) Moriones Jiménez, Paula; Echeverría Morrás, Jesús; Parra, Bernardo; Garrido Segovia, Julián José; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua
The aim of this research is to investigate the effect of phenyltriethoxysilane (PhTEOS) and tetraethoxysilane (TEOS) molar ratios as silicon precursors on the structure and porous texture of xerogels. We have prepared phenyl-silane hybrid xerogels from mixtures of PhTEOS and TEOS at pH 10 and 333 K, using ethanol as a solvent. Characterization techniques include 29Si NMR, FTIR, XRD, FE-SEM, HRTEM, TGA-DSC, helium density, and gas adsorption (N2 at 77 K and CO2 at 273 K). In order to assess the contribution of the quadrupolar moment of N2 and CO2 in the adsorption we obtained the adsorption– desorption isotherm of Ar at 87.3 K for the xerogel synthesized from 50% PhTEOS. The morphology of xerogels changed from aggregates of spherical particles for 20% PhTEOS to lamellae for samples obtained with PhTEOS percentages equal or larger that 60%. The incorporation of phenyl groups into the xerogel matrix caused an increase in the spacing bond between silicon atoms and led to an intramolecular reaction and the formation of lamellar domains. Increasing the PhTEOS molar ratio in the mixture of silicon precursors produced hybrid xerogels with lower specific surface area, pore volume and characteristic energy. The similarity between the isotherms of N2 at 77 K and Ar at 87.3 K indicates that the main retention mechanism is physisorption and that the variation in the surface chemistry with the incorporation of phenyl groups doesn’t inhibit the retention of N2.
Open Access
New hybrid organochlorinated xerogels
(2021) Cruz Quesada, Guillermo; Espinal Viguri, Maialen; López Ramón, María Victoria; Garrido Segovia, Julián José; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
Hybrid silica xerogels (HSXG) combine the properties of organic and inorganic components in the same material, which makes them promising and versatile candidates for multiple applications. These materials can be easily prepared by the sol-gel process, which offers the possibility to obtain different morphologies. The incorporation of organic precursors plays an important role in their properties, hence, allowing the design of materials for specific applications such as coatings for optical fibers [1]. The aim of this work was to study the influence of the alkyl chain and chlorine atom on the morphological and textural properties of various hybrid materials produced by co-condensation. For this purpose, three series of hybrid xerogels were prepared by co-condensation of TEOS and a chloroalkyltriethoxysilane (TEOS:ClRTEOS, R = methyl, ethyl or propyl) at different molar ratios. The influence of the precursors on the structure and textural properties of the xerogels was studied by means of N2 adsorption, XRD (X-ray diffraction), 29Si NMR (nuclear magnetic resonance) and FE-SEM (Field Emission-scanning electron microscope) [2].
Open Access
Volatile compounds other than CO2 emitted by different microorganisms promote distinct posttranscriptionally regulated responses in plants
(Wiley, 2019) García Gómez, Pablo; Almagro Zabalza, Goizeder; Sánchez López, Ángela María; Bahaji, Abdellatif; Ameztoy del Amo, Kinia; Ricarte Bermejo, Adriana; Baslam, Marouane; López Gómez, Pedro; Morán Juez, José Fernando; Garrido Segovia, Julián José; Muñoz Pérez, Francisco José; Baroja Fernández, Edurne; Pozueta Romero, Javier; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua
A 'box-in-box' cocultivation system was used to investigate plant responses to microbial volatile compounds (VCs) and to evaluate the contributions of organic and inorganic VCs (VOCs and VICs, respectively) to these responses. Arabidopsis plants were exposed to VCs emitted by adjacent Alternaria alternata and Penicillium aurantiogriseum cultures, with and without charcoal filtration. No VOCs were detected in the headspace of growth chambers containing fungal cultures with charcoal filters. However, these growth chambers exhibited elevated CO2 and bioactive CO and NO headspace concentrations. Independently of charcoal filtration, VCs from both fungal phytopathogens promoted growth and distinct developmental changes. Plants cultured at CO2 levels observed in growth boxes containing fungal cultures were identical to those cultured at ambient CO2. Plants exposed to charcoal-filtered fungal VCs, nonfiltered VCs, or superelevated CO2 levels exhibited transcriptional changes resembling those induced by increased irradiance. Thus, in the 'box-in-box'' system, (a) fungal VICs other than CO2 and/or VOCs not detected by our analytical systems strongly influence the plants' responses to fungal VCs, (b) different microorganisms release VCs with distinct action potentials, (c) transcriptional changes in VC-exposed plants are mainly due to enhanced photosynthesis signaling, and (d) regulation of some plant responses to fungal VCs is primarily posttranscriptional.
Open Access
Hybrid xerogels doped with Tb(III) and Eu (III) and a water soluble Pybox ligand
(2021) Cruz Quesada, Guillermo; Espinal Viguri, Maialen; Garrido Segovia, Julián José; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
Hybrid organic-inorganic siliceous materials (ORMOSiLs) are a key focus within the nanoscience area as they combine advantages of inorganic materials without losing characteristics intrinsic of organic molecules. In the past years, our research group has designed hybrid siliceous xerogels (HSXG) with porosities and surface chemistries on demand for a range of applications, such as coatings for optic fiber sensors [1]. Although hybrid xerogels are mainly amorphous materials, recent studies by our group have demonstrated that introducing specific organic fragments on the precursors can induce selforganization during the sol-gel process to obtain a series of transparent nanostructured HSXG [2]. In the present work, a step forward is taken in the applicability of this type of HSXG by doping them with Tb(III) or Eu (III) cations and a water-soluble pybox-based antenna ligand (Pybox-EG= 2,2′-(4-(2-Ethoxyethoxy)pyridine-2,6-diyl)bis(4,5-dihydrooxazole)). Inclusion of photoluminescence will provide the materials with new properties and therefore new applications in fiber optic sensors (FOS) or in solar cells devices.
Open Access
Hybrid xerogels: study of the sol-gel process and local structure by vibrational spectroscopy
(MDPI, 2021) Cruz Quesada, Guillermo; Espinal Viguri, Maialen; López Ramón, María Victoria; Garrido Segovia, Julián José; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The properties of hybrid silica xerogels obtained by the sol-gel method are highly dependent on the precursor and the synthesis conditions. This study examines the influence of organic substituents of the precursor on the sol-gel process and determines the structure of the final materials in xerogels containing tetraethyl orthosilicate (TEOS) and alkyltriethoxysilane or chloroalkyltri-ethoxysilane at different molar percentages (RTEOS and ClRTEOS, R = methyl [M], ethyl [E], or propyl [P]). The intermolecular forces exerted by the organic moiety and the chlorine atom of the precursors were elucidated by comparing the sol-gel process between alkyl and chloroalkyl series. The microstructure of the resulting xerogels was explored in a structural theoretical study using Fourier transformed infrared spectroscopy and deconvolution methods, revealing the distribution of (SiO)4 and (SiO)6 rings in the silicon matrix of the hybrid xerogels. The results demonstrate that the alkyl chain and the chlorine atom of the precursor in these materials determines their inductive and steric effects on the sol-gel process and, therefore, their gelation times. Furthermore, the distribution of (SiO)4 and (SiO)6 rings was found to be consistent with the data from the X-ray diffraction spectra, which confirm that the local periodicity associated with four-fold rings increases with higher percentage of precursor. Both the sol-gel process and the ordered domains formed determine the final structure of these hybrid materials and, therefore, their properties and potential applications.
Open Access
Determination of hazardous vapors from the thermal decomposition of organochlorinated silica xerogels with adsorptive properties
(Elsevier, 2024) Rosales Reina, María Beatriz; Cruz Quesada, Guillermo; Pujol, Pablo; Reinoso, Santiago; Elosúa Aguado, César; Arzamendi Manterola, Gurutze; López Ramón, María Victoria; Garrido Segovia, Julián José; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Institute of Smart Cities - ISC
The incorporation of organic groups into sol-gel silica materials is known to have a noticeable impact on the properties and structure of the resulting xerogels due to the combination of the properties inherent to the organic fragments (functionality and flexibility) with the mechanical and structural stability of the inorganic matrix. However, the reduction of the inorganic content in the materials could be detrimental to their thermal stability properties, limiting the range of their potential applications. Therefore, this work aims to evaluate the thermal stability of hybrid inorganic-organic silica xerogels prepared from mixtures of tetraethoxysilane and organochlorinated triethoxysilane precursors. To this end, a series of four materials with a molar percentage of organochlorinated precursor fixed at 10%, but differing in the type of organic group (chloroalkyls varying in the alkyl-chain length and chlorophenyl), has been selected as model case study. The gases and vapors released during the thermal decomposition of the samples under N2 atmosphere have been analyzed and their components determined and quantified using a thermogravimetric analyzer coupled to a Fourier-transform infrared spectrophotometer and to a gas chromatography-mass spectrometry unit. These analyses have allowed to identify up to three different thermal events for the pyrolysis of the organochlorinated xerogel materials and to elucidate the reaction pathways associated with such processes. These mechanisms have been found to be strongly dependent on the specific nature of the organic group.
Open Access
Kinetics of the acid-catalyzed hydrolysis of tetraethoxysilane (TEOS) by 29Si NMR spectroscopy and mathematical modeling
(Springer, 2018) Echeverría Morrás, Jesús; Moriones Jiménez, Paula; Arzamendi Manterola, Gurutze; Garrido Segovia, Julián José; Gil Idoate, María José; Cornejo Ibergallartu, Alfonso; Martínez Merino, Víctor; Química Aplicada; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2
Tetraethoxysilane (TEOS) is widely used to synthesize siliceous material by the sol–gel process. However, there is still some disagreement about the nature of the limiting step in the hydrolysis and condensation reactions. The goal of this research was to measure the variation in the concentration of intermediates formed in the acid-catalyzed hydrolysis by 29Si NMR spectroscopy, to model the reactions, and to obtain the rate constants and the activation energy for the hydrolysis and early condensation steps. We studied the kinetics of TEOS between pH 3.8 and 4.4, and four temperature values in the range of 277.2–313.2 K, with a TEOS:ethanol:water molar ratio of 1:30:20. Both hydrolysis and the condensation rate speeded up with the temperature and the concentration of oxonium ions. The kinetic constants for hydrolysis reactions increased in each step kh1 < kh2 < kh3 < kh4, but the condensation rate was lower for dimer formation than for the formation of the fully hydrolyzed Si(OH)4. The system was described according to 13 parameters: six of them for the kinetic constants estimated at 298.2 K, six to the activation energies, and one to the equilibrium constant for the fourth hydrolysis. The mathematical model shows a steady increase in the activation energy from 34.5 kJ mol−1 for the first hydrolysis to 39.2 kJ mol−1 in the last step. The activation energy for the condensation reaction from Si(OH)4 was ca. 10 kJ mol−1 higher than the largest activation energy in the hydrolytic reactions. The decrease in the net positive charge on the Si atom contributes to the protonation of the ethoxy group and makes it a better leaving group.
Open Access
Comprehensive kinetics of hydrolysis of organotriethoxysilanes by 29Si NMR
(American Chemical Society, 2019) Moriones Jiménez, Paula; Arzamendi Manterola, Gurutze; Cornejo Ibergallartu, Alfonso; Garrido Segovia, Julián José; Echeverría Morrás, Jesús; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
The kinetics of several representative hybrid precursors were studied via 29Si NMR: three alkyl precursors, methyltriethoxysilane, ethyltriethoxysilane, and propyltriethoxysilane; as well as two unsaturated radicals, vinyltriethoxysilane and phenyltriethoxysilane. The reaction rate is related to the chemical shift of 29Si in the NMR spectra, which gives information about the electronic density of the Si atoms and the inductive effects of substituents. The concentration of the precursors decreased exponentially with time, and the intermediate products of hydrolysis and the beginning of the condensation reactions showed curves characteristic of sequential reactions, with a similar distribution of the species as a function of the fractional conversion. For all of the precursors, condensation started when the most hydrolyzed species reached a maximum concentration of 0.30 M, when the precursor had run out. A prediction following the developed mathematical model fits the experimental results in line with a common pathway described by eight parameters.
Open Access
Tunability of hybrid silica xerogels: surface chemistry and porous texture based on the aromatic precursor
(MDPI, 2023) Rosales Reina, María Beatriz; Cruz Quesada, Guillermo; Padilla-Postigo, Nataly; Irigoyen-Razquin, Marian; Alonso-Martínez, Ester; López Ramón, María Victoria; Espinal Viguri, Maialen; Garrido Segovia, Julián José; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The interest in new materials with specific properties has increased because they are essential for the environmental and technological needs of our society. Among them, silica hybrid xerogels have emerged as promising candidates due to their simple preparation and tunability: when they are synthesised, depending on the organic precursor and its concentration, their properties can be modulated, and thus, it is possible to prepare materials with à la carte porosity and surface chemistry. This research aims to design two new series of silica hybrid xerogels by co-condensation of tetraethoxysilane (TEOS) with triethoxy(p-tolyl)silane (MPhTEOS) or 1,4-bis(triethoxysilyl)benzene (Ph(TEOS)2 and to determine their chemical and textural properties based on a variety of characterisation techniques (FT-IR, 29Si NMR, X-ray diffraction and N2 , CO2 and water vapour adsorption, among others). The information gathered from these techniques reveals that depending on the organic precursor and its molar percentage, materials with different porosity, hydrophilicity and local order are obtained, evidencing the easy modulation of their properties. The ultimate goal of this study is to prepare materials suitable for a variety of applications, such as adsorbents for pollutants, catalysts, films for solar cells or coatings for optic fibre sensors.