Synthesis and Structural Characterization of Branched Bimetallic AuPd Nanoparticles with a Highly Tunable Optical Response

Bimetallic nanostructures composed of gold (Au) and palladium (Pd) have garnered increased interest for their applications in heterogeneous catalysis. This study reports a simple strategy for manufacturing Au@Pd bimetallic branched nanoparticles (NPs), which offer a tunable optical response, using polyallylamine-stabilized branched AuNPs as template cores for Pd overgrowth. The palladium content can be altered by manipulating the concentration of PdCl4 2− and ascorbic acid (AA) that are injected, which permit an overgrowth of the Pd shell up to ca. 2 nm thick. The homogeneous distribution of Pd at the surfaces of Au NPs can be carried out regardless of their size or branching degree, which allows for an adjustment of the plasmon response in the near-infrared (NIR) spectral range. As a proof of concept, the nanoenzymatic activity of pure gold and gold−palladium NPs was compared, exploring their peroxidase-like activity in the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). The bimetallic AuPd NPs demonstrate an increase in the catalytic properties attributed to the presence of palladium at the surface of gold

Synthesis of gold functionalised nanoparticles with the eranthis hyemalis lectin and preliminary toxicological studies on caenorhabditis elegans

The lectin found in the tubers of the Winter Aconite (Eranthis hyemalis) plant (EHL) is a Type II Ribosome Inactivating Protein (RIP). Type II RIPs have shown anti-cancer properties and have great potential as therapeutic agents. Similarly, colloidal gold nanoparticles are successfully used in biomedical applications as they can be functionalised with ligands with high affinity and specificity for target cells to create therapeutic and imaging agents. Here we present the synthesis and characterization of gold nanoparticles conjugated with EHL and the results of a set of initial assays to establish whether the biological effect of EHL is altered by the conjugation. Gold nanoparticles functionalised with EHL (AuNPs@EHL) were successfully synthesised by bioconjugation with citrate gold nanoparticles (AuNPs@Citrate). The conjugates were analysed by UV-Vis spectroscopy, Dynamic Light Scattering (DLS), Zeta Potential analysis, and Transmission Electron Microscopy (TEM). Results indicate that an optimal functionalisation was achieved with the addition of 100 µL of EHL (concentration 1090 ± 40 µg/mL) over 5 mL of AuNPs (concentration [Au0] = 0.8 mM). Biological assays on the effect of AuNPs@EHL were undertaken on Caenorhabditis elegans, a free-living nematode commonly used for toxicological studies, that has previously been shown to be strongly affected by EHL. Citrate gold nanoparticles did not have any obvious effect on the nematodes. For first larval stage (L1) nematodes, AuNPs@EHL showed a lower biological effect than EHL. For L4 stage, pre-adult nematodes, both EHL alone and AuNPs@EHL delayed the onset of reproduction and reduced fecundity. These assays indicate that EHL can be conjugated to gold nanoparticles and retain elements of biocidal activity

Una aproximación estadística al estudio de la carbonatación del hormigón

Carbonation is one of the factors that conditions reinforced concrete durability, while porosity is one of the parameters that determines the carbonation rate: as a rule, the greater the porosity, the higher the rate. While many papers have been published on the effect of CO2 penetration in the pore solutions of concretes prepared under different experimental conditions, the literature has yet to address the joint effect of the factors considered in concrete design, such as the water/cement (w/c) ratio, type of cement, type of aggregate and presence of admixtures. The present paper discusses the findings of a statistical study of the impact of the aforementioned factors on both system porosity and carbonation rate. The type of cement, individually and in its interaction with the rest of the factors, proved to be the major determinant in concrete carbonation.La carbonatación es uno de los factores que supedita la durabilidad del hormigón armado, siendo la porosidad uno de los parámetros que más condicionan la velocidad de carbonatación. Son muchos los trabajos que estudian el efecto de la penetración del CO2 en la solución de los poros de hormigones preparados bajo distintas condiciones experimentales, sin embargo, no se encuentran referencias que analicen de forma conjunta el efecto de ciertos factores como son la relación agua/cemento (a/c ratio), el tipo de cemento, el tipo de árido y la presencia de aditivos, normalmente consideradas a la hora de diseñar un hormigón. En este trabajo se discuten los resultados obtenidos tras realizar un estudio estadístico del efecto que tienen los factores previamente mencionados, tanto en la porosidad de estos sistemas como en su nivel de carbonatación. El cemento tanto de manera individual como en sus interacciones con el resto de los factores es el factor que mas afecta a la carbonatación del hormigón

Influence of calcium aluminate cement (CAC) on alkaline activation of red clay brick waste (RCBW)

In this paper, the effect of calcium aluminate cement (CAC) additions on the alkali activation of red clay brick waste (RCBW) was studied at room temperature and at 65 C. RCBW was partially replaced with CAC (0e50 wt.%) and blends were activated with NaOH and sodium silicate solutions. The compressive strength evolution was tested on mortars and the nature of the reaction products was analysed by infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, microscopic studies and pH measurements. The results show that the use of CAC accelerates the activation process of RCBW so that 50 MPa were obtained in the blended mortars containing 40 wt.% CAC cured for 3 days at room temperature. CAC did not undergo normal hydration and only the C3AH6 phase was identified in the pastes blended with more than 30 wt.% CAC and cured at 65 C, while the main reaction product was a cementitious gel containing Ca and Al from CAC.The authors are grateful to the Spanish Ministry of Science and Innovation for supporting this study through Project GEOCEDEM BIA 2011-26947, and to FEDER funding.Reig Cerdá, L.; Soriano Martínez, L.; Borrachero Rosado, MV.; Monzó Balbuena, JM.; Paya Bernabeu, JJ. (2016). Influence of calcium aluminate cement (CAC) on alkaline activation of red clay brick waste (RCBW). Cement and Concrete Composites. 65:177-185. https://doi.org/10.1016/j.cemconcomp.2015.10.021S1771856

Influence of the activator concentration and calcium hydroxide addition on the properties of alkali-activated porcelain stoneware

Objective The aim of this research was to investigate the influence of the alkali activator concentration and calcium dosage on the fresh behavior, compressive strength and microstructure of the binder produced by the alkali activation of porcelain stoneware waste, using NaOH and sodium silicate solution as activators. Materials Porcelain stoneware waste, NaOH and sodium silicate. Method Tested properties of mortars were the compressive strength and the setting times. Thermogravimetric analyses, microscopic studies, pH measurements, XRD and FTIR tests were used to assess the evolution of the microstructure developed. Results The results show that the activator concentration and calcium to sodium molar ratio strongly influence the fresh behavior and the hardening process of mortars. A linear evolution of compressive strength with sodium addition was observed when keeping the SiO2 concentration constant. Mortar samples with up to 36 MPa under compression were obtained after curing for 7 days at 65 °C.The authors are grateful to the Spanish Ministry of Science and Innovation for supporting this study through Project GEOCEDEM BIA 2011-26947, and to FEDER funding.Reig Cerdá, L.; Soriano Martínez, L.; Borrachero Rosado, MV.; Monzó Balbuena, JM.; Paya Bernabeu, JJ. (2014). Influence of the activator concentration and calcium hydroxide addition on the properties of alkali-activated porcelain stoneware. Construction and Building Materials. 63:214-222. https://doi.org/10.1016/j.conbuildmat.2014.04.023S2142226

Ultrasonic energy for proteomics: when, where and how

Comunicaciones a congreso

Leaching behaviour of cement encapsulated thermally treated organic ion exchange resins

Cementation in OPC is a widely accepted method for the conditioning of Spent Ion Exchange Resins (IERs). However, the resulting waste forms tends to crack due to the induced forces by IERs swelling upon the adsorption of water. Pre-treatments, such as pyrolysis and incineration, are effective ways to minimize resin swelling issues, besides providing a significant volume reduction. In the present work, immobilization of ashes resulting from the thermal treatment of IERs was performed into three selected cement matrices of CEM I, CEM III and one-part geopolymer; the latter based on metakaolin, blast furnace slag and sodium silicate. By means of a series of batch experiments, the leaching behaviour of the waste/matrix system was assessed. Prismatic probes of 1×1×6 cm3 for each cement matrix, encapsulating 0 (reference) and 20 wt.% of the IERs ashes, were immersed in either a) deionized water, b) in situ disposal site water from El Cabril, the Spanish disposal facility for very low, low and intermediate level radioactive waste, and c) synthetic cementitious water, for reasons of leaching comparison in agreement with the ISO 6961 standard [1]. The ratio between the external surface area of the cement probes and the volume of solution was set to 0.1. All solutions were renovated every week for the first month and then every month up to 180 days. Monitoring of pH, electrical conductivity (EC) and concentrations of main and trace elements in solution were carried out. In general, no significant changes in pH were observed in the experiments performed with cementitious water as the pH was controlled by the initial pH of the solution (12.7). The pH in experiments with deionized and in situ waters increased rapidly from 7 to values in the range 10-11 (depending on the cement matrix composition) over the first week, and then stabilized into a steady range. However, the pH in samples with geopolymer decreased continuously to a range within 9.5-10 and does not seem to have reached a steady stage after 6 months. Similar trends were observed in the leaching behaviour of main cations (Ca, Na, K, Al, and Si) from the reference and IERs-containing cement probes but, as for pH, in general, steady stage was not reached. Additionally, in experiments with sampled water in El Cabril, oxidation-reduction potential was monitored and TOC in solution was measured, confirming no release of organics. Limited leaching of doping elements was observed. The joined evaluation of data may contribute to help to assess the potential of the three candidate materials a suitable conditioning matri

Crustal Imbrication in an Alpine Intraplate Mountain Range: A Wide-Angle Cross-Section Across the Spanish-Portuguese Central System

Intraplate ranges are topographic features that can occur far from plate boundaries, the expected position of orogens as described in the plate tectonics theory. To understand the lithospheric structure of intraplate ranges, we focused on the Spanish-Portuguese Central System (SPCS), the most outstanding topographic feature in the central Iberian Peninsula. The SPCS is an Alpine range that exhumes Precambrian-Paleozoic rocks and is located at >200 km from the northern border of the Iberian microplate. Here, we provide a P-wave velocity model based on wide-angle seismic reflection/refraction data of the central SPCS (Gredos sector). Our results show: (a) a layered lithosphere characterized by three major interfaces: Conrad, Mohorovicic, and Hales discontinuities, (b) an asymmetry of the crust-mantle boundary under the SPCS, (c) the extent of the Variscan batholith forming the main outcrops of Gredos, and (d) the thinning of the lower crust toward the south. This model suggests that the exhumation of the SPCS basement was driven by a south-vergent thick-skinned thrust system, developed in the southern part of the SPCS and that promoted crustal imbrication and a Mohorovicic discontinuity's offset under the SPCS. Thus, the deformation mechanisms of the crust seem to be controlled by the presence of the late- to post-Variscan granitoids that assimilated the Variscan mid-crustal detachment creating a new rheological boundary. This tectonic structure allowed the formation of Alpine crustal-scale thrust systems that eased coupled deformation of the upper and lower crust, leading to limited underthrusting of both crustal layers.This study has been funded by the Ministry of Science, Innovation and Competitiveness through the Project CIMDEF (CGL2014-56548-P). IP is funded by the Spanish Government and the University of Salamanca (Beatriz Galindo grant BEGAL 18/00090). JA is funded by grant IJC2018-036074-I, funded by MCIN/AEI/10.13039/501100011033. DMP and FGL are also funded by grants CGL2015-71692 (MINECO/ FEDER) and PID2020-118822GB-I00 (MCIN/AEI/10.13039/501100011033).Peer reviewe

Alkali activation of vitreous calcium aluminosilicate derived from glass fiber waste

The properties and microstructure of alkali-activated (AA) vitreous calcium aluminosilicate (VCAS) are presented in this paper. VCAS is manufactured from a by-product of the glass fiber industry and has been activated using NaOH and KOH solutions. The microstructure and mechanical properties of AA VCAS pastes and mortars are reported. The results show that depending on the type and concentration of hydroxide solution used, mortar samples with compressive strengths up to 77 MPa can be formed after curing for three days at 65 °C. The research demonstrates the potential of VCAS to produce AA cements and the importance of alkali type and concentration in optimizing properties and microstructure.Mitsuuchi Tashima, M.; Soriano Martinez, L.; Borrachero Rosado, MV.; Monzó Balbuena, JM.; Cheeseman, CR.; Paya Bernabeu, JJ. (2012). Alkali activation of vitreous calcium aluminosilicate derived from glass fiber waste. Journal of Sustainable Cement-Based Materials. 1(3):83-93. doi:10.1080/21650373.2012.742610S839313Mahasenan N, Smith S, Humphreys K. The cement industry and global climate change: current and potential future cement industry CO2emissions. Greenhouse Gas Control Technologies – 6th International Conference. Oxford: Pergamon; 2003. p. 995–1000.Schneider, M., Romer, M., Tschudin, M., & Bolio, H. (2011). Sustainable cement production—present and future. Cement and Concrete Research, 41(7), 642-650. doi:10.1016/j.cemconres.2011.03.019WBCSD – World Business Council for Sustainable Development. Cement industry energy and CO2performance – Getting numbers right. Edited by WBCSD, Geneva-Switzerland (ISBN 978-3-940388-48-3). 2009.Shi, C., Jiménez, A. F., & Palomo, A. (2011). New cements for the 21st century: The pursuit of an alternative to Portland cement. Cement and Concrete Research, 41(7), 750-763. doi:10.1016/j.cemconres.2011.03.016Duxson, P., Fernández-Jiménez, A., Provis, J. L., Lukey, G. C., Palomo, A., & van Deventer, J. S. J. (2006). Geopolymer technology: the current state of the art. Journal of Materials Science, 42(9), 2917-2933. doi:10.1007/s10853-006-0637-zFernández-Jiménez, A., Palomo, A., & Criado, M. (2005). Microstructure development of alkali-activated fly ash cement: a descriptive model. Cement and Concrete Research, 35(6), 1204-1209. doi:10.1016/j.cemconres.2004.08.021Hossain, A. B., Shirazi, S. A., Persun, J., & Neithalath, N. (2008). Properties of Concrete Containing Vitreous Calcium Aluminosilicate Pozzolan. Transportation Research Record: Journal of the Transportation Research Board, 2070(1), 32-38. doi:10.3141/2070-05Neithalath, N., Persun, J., & Hossain, A. (2009). Hydration in high-performance cementitious systems containing vitreous calcium aluminosilicate or silica fume. Cement and Concrete Research, 39(6), 473-481. doi:10.1016/j.cemconres.2009.03.006Tashima MM, Soriano L, Borrachero MV, Monzó J, Payá J. Effect of curing time on the microstructure and mechanical strength development of alkali activated nbinders based on vitreous calcium aluminosilicate (VCAS). Bull. Mater. Sci. in press.Hemmings RT, Nelson RD, Graves PL, Cornelius BJ. White pozzolan composition and blended cements containing same. Patent US6776838. 2004.Provis, J. L., Lukey, G. C., & van Deventer, J. S. J. (2005). Do Geopolymers Actually Contain Nanocrystalline Zeolites? A Reexamination of Existing Results. Chemistry of Materials, 17(12), 3075-3085. doi:10.1021/cm050230iCriado, M., Fernández-Jiménez, A., de la Torre, A. G., Aranda, M. A. G., & Palomo, A. (2007). An XRD study of the effect of the SiO2/Na2O ratio on the alkali activation of fly ash. Cement and Concrete Research, 37(5), 671-679. doi:10.1016/j.cemconres.2007.01.013Rees, C. A., Provis, J. L., Lukey, G. C., & van Deventer, J. S. J. (2007). In Situ ATR-FTIR Study of the Early Stages of Fly Ash Geopolymer Gel Formation. Langmuir, 23(17), 9076-9082. doi:10.1021/la701185gLee, W. K. W., & van Deventer, J. S. J. (2003). Use of Infrared Spectroscopy to Study Geopolymerization of Heterogeneous Amorphous Aluminosilicates. Langmuir, 19(21), 8726-8734. doi:10.1021/la026127eGarcía-Lodeiro, I., Fernández-Jiménez, A., Blanco, M. T., & Palomo, A. (2007). FTIR study of the sol–gel synthesis of cementitious gels: C–S–H and N–A–S–H. Journal of Sol-Gel Science and Technology, 45(1), 63-72. doi:10.1007/s10971-007-1643-6Barbosa VFF. Sintese e caracterização de polissialatos (Synthesis and characterization of polysialates) [PhD thesis] (in Portuguese). Instituto Militar de Engenharia. Rio de Janeiro - Brazil. 190 p. 1999.Bernal, S. A., Rodríguez, E. D., Mejía de Gutiérrez, R., Gordillo, M., & Provis, J. L. (2011). Mechanical and thermal characterisation of geopolymers based on silicate-activated metakaolin/slag blends. Journal of Materials Science, 46(16), 5477-5486. doi:10.1007/s10853-011-5490-zBoccaccini, A. R., Bücker, M., Bossert, J., & Marszalek, K. (1997). Glass matrix composites from coal flyash and waste glass. Waste Management, 17(1), 39-45. doi:10.1016/s0956-053x(97)00035-4Kourti, I., Rani, D. A., Deegan, D., Boccaccini, A. R., & Cheeseman, C. R. (2010). Production of geopolymers using glass produced from DC plasma treatment of air pollution control (APC) residues. Journal of Hazardous Materials, 176(1-3), 704-709. doi:10.1016/j.jhazmat.2009.11.089Lampris, C., Lupo, R., & Cheeseman, C. R. (2009). Geopolymerisation of silt generated from construction and demolition waste washing plants. Waste Management, 29(1), 368-373. doi:10.1016/j.wasman.2008.04.007Wu, H.-C., & Sun, P. (2007). New building materials from fly ash-based lightweight inorganic polymer. Construction and Building Materials, 21(1), 211-217. doi:10.1016/j.conbuildmat.2005.06.052Kourti, I., Amutha Rani, D., Boccaccini, A. R., & Cheeseman, C. R. (2011). Geopolymers from DC Plasma–Treated Air Pollution Control Residues, Metakaolin, and Granulated Blast Furnace Slag. Journal of Materials in Civil Engineering, 23(6), 735-740. doi:10.1061/(asce)mt.1943-5533.000017