48 results on '"M. Luisa Ferrer"'
Search Results
2. Aqueous Co-Solvent in Zwitterionic-based Protic Ionic Liquids as Electrolytes in 2.0 V Supercapacitors
- Author
-
Sofia Calero, José Manuel Vicent-Luna, Francisco del Monte, Xuejun Lu, María C. Gutiérrez, María J. Roldán-Ruiz, M. Luisa Ferrer, Ricardo Jiménez, Center for Computational Energy Research, Materials Simulation & Modelling, Computational Materials Physics, Molecular Simulation & Modelling, EIRES Systems for Sustainable Heat, and EIRES Chem. for Sustainable Energy Systems more...
- Subjects
General Chemical Engineering ,02 engineering and technology ,Electrolyte ,room-temperature protic ionic liquids ,010402 general chemistry ,Electrochemistry ,01 natural sciences ,Miscibility ,chemistry.chemical_compound ,Ethanolamine ,Environmental Chemistry ,supercapacitor cells ,General Materials Science ,SDG 7 - Affordable and Clean Energy ,Aqueous solution ,021001 nanoscience & nanotechnology ,zwitterions ,0104 chemical sciences ,General Energy ,chemistry ,Zwitterion ,Ionic liquid ,electrochemical stability window ,Physical chemistry ,water-in-salt electrolytes ,0210 nano-technology ,SDG 7 – Betaalbare en schone energie ,Stoichiometry - Abstract
High-performance energy-storage devices are receiving great interest in sustainable terms as a required complement to renewable energy sources to level out the imbalances between supply and demand. Besides electrode optimization, a primary objective is also the judicious design of high-performance electrolytes combining novel ionic liquids (ILs) and mixtures of aqueous solvents capable of offering “à la carte” properties. Herein, it is described the stoichiometric addition of a zwitterion such as betaine (BET) to protic ILs (PILs) such as those formed between methane sulfonic acid (MSAH) or p-toluenesulfonic acid (PTSAH) with ethanolamine (EOA). This addition resulted in the formation of zwitterionic-based PILs (ZPILs) containing the original anion and cation as well as the zwitterion. The ZPILs prepared in this work ([EOAH]+[BET][MSA]− and [EOAH]+[BET][PTSA]−) were liquid at room temperature even though the original PILs ([EOAH]+[MSA]− and [EOAH]+[PTSA]−) were not. Moreover, ZPILs exhibited a wide electrochemical stability window, up to 3.7 V vs. Ag wire for [EOAH]+[BET][MSA]− and 4.0 V vs. Ag wire for [EOAH]+[BET][PTSA]− at room temperature, and a high miscibility with both water and aqueous co-solvent (WcS) mixtures. In particular, “WcS-in-ZPIL” mixtures of [EOAH]+[BET][MSA]− in 2 H2O/ACN/DMSO provided specific capacitances of approximately 83 F g−1 at current densities of 1 A g−1, and capacity retentions of approximately 90 % after 6000 cycles when operating at a voltage of 2.0 V and a current density of 4 A g−1. more...
- Published
- 2020
Catalog
3. EMIMBF4 in ternary liquid mixtures of water, dimethyl sulfoxide and acetonitrile as 'tri-solvent-in-salt' electrolytes for high-performance supercapacitors operating at -70 °C
- Author
-
Rafael M. Madero-Castro, María C. Gutiérrez, José Manuel Vicent-Luna, M. Luisa Ferrer, Sofia Calero, Francisco del Monte, Xuejun Lu, Materials Simulation & Modelling, Computational Materials Physics, Molecular Simulation & Modelling, EIRES Systems for Sustainable Heat, and EIRES Chem. for Sustainable Energy Systems more...
- Subjects
Materials science ,Inorganic chemistry ,Energy Engineering and Power Technology ,Salt (chemistry) ,02 engineering and technology ,Electrolyte ,010402 general chemistry ,Electrochemistry ,01 natural sciences ,chemistry.chemical_compound ,Supercapacitors ,General Materials Science ,SDG 7 - Affordable and Clean Energy ,Acetonitrile ,Eutectic system ,Supercapacitor ,chemistry.chemical_classification ,Renewable Energy, Sustainability and the Environment ,Eutectic mixtures ,Solvent-in-salt electrolytes ,021001 nanoscience & nanotechnology ,Water-in-salt electrolytes ,0104 chemical sciences ,Solvent ,chemistry ,Ionic liquid ,Hydrogen bond complexes ,0210 nano-technology ,SDG 7 – Betaalbare en schone energie - Abstract
For many years, the performance of Li-ion batteries (LIBs) and supercapacitors (SCs) has relied mainly on two factors, (1) the optimization of electrodes composition and/or structure and (2) the selection of salts or ionic liquids (ILs) matching well with the compositional and/or structural features of electrodes. Solvents included in electrolyte composition have been typically seen as a mere medium where the electrochemically active salts or ILs are dissolved or mixed. More recently, attention has also been paid to specific issues, such as flammability, toxicity, electrical conductivity and/or electrochemical stability window (ESW). Recent reports describing water-in-salt (WIS), solvent-in-salt (SIS) and bi-solvent-in-salt (BSIS) electrolytes demonstrated that solvent molecules may indeed play a more active role in the achievement of high-performance LIBs and SCs. This work accomplished the design of a tri-solvent-in-salt (TSIS) electrolyte where every solvent contributed (with an IL such as EMIMBF4) to the formation of an electrochemically active hydrogen bond (HB) complex structure. Raman and NMR spectroscopies, as well as molecular dynamic (MD) simulations helped elucidate the ratio among all compounds (e.g., solvents and IL) in the HB complex structure that best works as an electrolyte. For instance, one could start from the eutectic mixture of H2O and dimethylsulfoxide (DMSO) in a 2 to 1 molar ratio and then add acetonitrile (CH3CN) in different molar ratios. Thus, the 2H2O:DMSO mixture offers low melting point and low flammability, and CH3CN provides an improvement of the rate capability to the resulting electrolyte. As compared to other electrolytes, the TSIS electrolyte composed of 1.5EMIMBF4:2H2O:DMSO:3.5CH3CN (5.8 m, TSIS-5.8) was cost efficient and exhibited self-extinction rates as low as 40 s g-1. Moreover, SCs operating with TSIS-5.8, at -70 °C and up to 2.7 V provided energy densities of ca. 49 and 18 Wh kg-1 at, respectively, power densities of 10,000 and 17,000 W kg-1, a capacitance retention of ca. 82% after 15,000 cycles at 4 A g-1 and a self-discharge as low as 22%. more...
- Published
- 2021
4. 'Tri-Solvent-in-Salt' Electrolytes for High-Performance Supercapacitors
- Author
-
Xuejun Lu, María C Gutiérrez, M. Luisa Ferrer, and Jian Liu
- Abstract
Electrolytes chemistry for high-performance supercapacitors (SCs) has been addressed recently, where solvents included in electrolyte composition dissolving or mixing the electrochemically active salts or ILs have been typically seen as a mere medium.[1] Specifically, attention regarding the achievement of high-performacne SCs has also been paid to, e.g., water-in-salt (WIS), solvent-in-salt (SIS), and bi-solvent-in-salt (BSIS) electrolytes, demonstrating that solvent molecules may indeed play a more active role.[2 - 4] In this presentation, we will talk about the design of a tri-solvent-in-salt (TSIS) electrolyte where every solvent contributed (with an IL, i.e., EMIMBF4) to the formation of an electrochemically active hydrogen bond (HB) complex structure. Raman and NMR spectroscopies, as well as molecular dynamic (MD) simulations, helped elucidate the ratio among all compounds (e.g., solvents and IL) in the HB complex structure that best works as an electrolyte. For instance, the eutectic mixture of H2O and dimethylsulfoxide (DMSO) in a 2 to 1 molar ratio primary HB complex structures with mixed EMIMBF4 offers a low melting point and low flammability, then add acetonitrile (CH3CN) in different molar ratios providing an improvement of the rate capability to the resulting electrolyte. As compared to other electrolytes, the TSIS electrolyte composed in a molality of 5.8 m (TSIS-5.8) showed the cost efficiency and exhibited a low self-extinction rate. Moreover, SCs operating with TSIS-5.8, at -70 °C and up to 2.7 V provided energy densities of ca. 49 and 18 Wh kg-1, respectively, power densities of 10,000 and 17,000 W kg-1, the capacitance retention of ca. 82% after 15,000 cycles at 4 A g-1 and a self-discharge as low as 22%. The use of ternary solvent mixtures combining different solvents in the proper molar ratios opens up an easy and low-cost path to design many new electrolytes in terms of non-flammability, non-toxicity, high electrical conductivity, and wide electrochemical stability window (ESW). Forthcoming research could use the knowledge provided by this work in terms of ions solvation and transport in TSIS electrolytes and explore the interfacial interactions between electrolyte and electrode material to determine their respective relevance in the performance of SCs. Keywords: tri-solvent-in-salt (TSIS), hydrogen bond, eutectic mixtures, supercapacitors Reference : [1] F. Béguin, et al. Carbons and electrolytes for advanced supercapacitors. Adv. Mater., 26 (2014), 2219-2251. [2] Q. Dou, et al. Safe and high-rate supercapacitors based on an ‘‘Acetonitrile/Water in Salt’’ hybrid electrolyte. Energy Environ. Sci, 11 (2018), 3212-3219. [3] X. Lu, et al. Aqueous-Eutectic-in-Salt Electrolytes for High-Energy-Density Supercapacitors with an Operational Temperature Window of 100 °C, from −35 to +65 °C. ACS Appl. Mater. Interfaces 2020, 12, 26, 29181–29193. [4] X. Lu, et al. Aqueous Co-Solvent in Zwitterionic-based Protic Ionic Liquids as Electrolytes in 2.0 V Supercapacitors. ChemSusChem 2020, 13, 5983. [5] X. Lu, et al. EMIMBF4 in ternary liquid mixtures of water, dimethyl sulfoxide and acetonitrile as “tri-solvent-in-salt” electrolytes for high-performance supercapacitors operating at -70 °C. Energy Storage Mater., 40, (2021), 368-385. more...
- Published
- 2022
- Full Text
- View/download PDF
5. Iron Phthalocyanine-Knitted Polymers as Electrocatalysts for the Oxygen Reduction Reaction
- Author
-
Antonio Valverde-González, Marta Iglesias, M. Luisa Ferrer, Eva M. Maya, Li-Zhi Guan, and Ministerio de Ciencia, Innovación y Universidades (España)
- Subjects
chemistry.chemical_classification ,Materials science ,010405 organic chemistry ,Iron phthalocyanine ,Iron (II) phthalocyanine ,Single step ,Polymer ,Electrocatalyst ,010402 general chemistry ,01 natural sciences ,Oxygen reduction reaction ,0104 chemical sciences ,chemistry.chemical_compound ,Monomer ,Chemical engineering ,chemistry ,General Materials Science ,Knitting porous polymer ,Porosity - Abstract
[EN] Knitted iron phthalocyanine-based porous polymer networks (K-FePcs) were prepared in a single step using solvent-knitting strategies with commercial iron phthalocyanine as a building monomer. The incorporation of different aryl comonomers (biphenyl and 1,2,4,5-tetraphenylbenzene) to FePc allowed quantitative yields, high porosities, and excellent ORR activity. The reversible Fe(III)/Fe(II) redox potential of FeN4 centers of the knitted polymer networks in N2-saturated electrolyte solution (i.e., ∼0.8 V vs RHE) were shown as good descriptors of their ORR activity. K-FePc2Ph presented the highest amount of FeN4 active sites and an adequate degree of steric hindrance to maintain the isolation between catalytically active sites. Moreover, it displayed comparable current density limits and superior mass activity and half-wave potential (i.e., 0.88 V vs RHE) than those of 20% Pt/C benchmark catalyst, while keeping higher stability toward methanol oxidation. K-FePc2Ph can be an interesting alternative to Pt-based ORR electrocatalysts., The authors acknowledge MINECO of Spain MAT2017-82288-C2-2-P and RTI2018-097728-B-I00 projects for financial support. A.V.-G. thanks Ministerio de Educación y Formación Profesional for FPU17/03463. L.Z.G. also acknowledges the Chinese Scholarship Council for a PhD research fellowship (CSC no. 201608330266). more...
- Published
- 2020
6. Aqueous-Eutectic-in-Salt Electrolytes for High-Energy-Density Supercapacitors with an Operational Temperature Window of 100 °C, from −35 to +65 °C
- Author
-
María C. Gutiérrez, Dónal Leech, Francisco del Monte, Rafael J. Jiménez-Riobóo, M. Luisa Ferrer, and Xuejun Lu
- Subjects
Aqueous solution ,Materials science ,Precipitation (chemistry) ,Ionic transfer ,02 engineering and technology ,Electrolyte ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Boiling point ,Chemical engineering ,Melting point ,General Materials Science ,0210 nano-technology ,Dissolution ,Eutectic system - Abstract
Water-in-salt (WIS) electrolytes are gaining increased interest as an alternative to conventional aqueous or organic ones. WIS electrolytes offer an interesting combination of safety, thanks to their aqueous character, and extended electrochemical stability window, thanks to the strong coordination between water molecules and ion salt. Nonetheless, cost, the tendency of salt precipitation, and sluggish ionic transfer leading to poor rate performance of devices are some intrinsic drawbacks of WIS electrolytes that yet need to be addressed for their technological implementation. It is worth noting that the absence of "free'' water molecules could also be achieved via the addition of a certain cosolvent capable of coordinating with water. This is the case of the eutectic mixture formed between DMSO and H2O with a molar ratio of 1:2 and a melting point as low as -140 °C. Interestingly, addition of salts at near-saturation conditions also resulted in an increase of the boiling point of the resulting solution. Herein, we used a eutectic mixture of DMSO and H2O for dissolution of LiTFSI in the 1.1-8.8 molality range. The resulting electrolyte (e.g., the so-called aqueous-eutectic-in-salt) exhibited excellent energy and power densities when operating in a supercapacitor cell over a wide range of extreme ambient temperatures, from as low as -35 °C to as high as +65 °C. more...
- Published
- 2020
- Full Text
- View/download PDF
7. Brillouin Spectroscopy as a Suitable Technique for the Determination of the Eutectic Composition in Mixtures of Choline Chloride and Water
- Author
-
Rafael J. Jiménez-Riobóo, Francisco del Monte, Huan Zhang, María C. Gutiérrez, María J. Roldán-Ruiz, and M. Luisa Ferrer
- Subjects
Materials science ,Brillouin Spectroscopy ,010304 chemical physics ,Inorganic chemistry ,010402 general chemistry ,01 natural sciences ,Acceptor ,0104 chemical sciences ,Surfaces, Coatings and Films ,chemistry.chemical_compound ,chemistry ,0103 physical sciences ,Materials Chemistry ,Physical and Theoretical Chemistry ,Choline chloride ,Eutectic system - Abstract
Deep eutectic solvents (DESs) resulting from the right combination between a hydrogen-bond donor (HBD) and a hydrogen-bond acceptor (HBA) are becoming quite popular in number of applications. More recently, natural DESs (NADESs) containing sugars, natural organic acids, and amino acids as HBDs and ChCl as HBA have received great attention because of their further environmental sustainability as compared to regular DESs. Within this context, mixing water in controlled amounts has been widely accepted as a simple and practical way of altering DES chemical and thermodynamic properties, with viscosity and conductivity experiencing the most significant changes. However, the number of papers describing eutectic mixtures with water as the only HBD is scarce and basically none has been done in fundamental terms. Herein, we investigated mixtures composed of water as the only HBD and ChCl as the HBA using differential scanning calorimetry (DSC) as well as more...
- Published
- 2020
8. Favorable Biological Responses of Neural Cells and Tissue Interacting with Graphene Oxide Microfibers
- Author
-
Jorge E. Collazos-Castro, Ankor González-Mayorga, Francisco del Monte, M. Luisa Ferrer, María Concepción Serrano, Elisa López-Dolado, María C. Gutiérrez, Ministerio de Economía y Competitividad (España), Instituto de Salud Carlos III, and European Commission more...
- Subjects
business.product_category ,Materials science ,General Chemical Engineering ,Oxide ,neural progenitor cells ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Article ,Neural tissue engineering ,law.invention ,lcsh:Chemistry ,chemistry.chemical_compound ,microfiber ,In vivo ,law ,Microfiber ,medicine ,Neural Growth ,Spinal cord injury ,Graphene ,General Chemistry ,021001 nanoscience & nanotechnology ,medicine.disease ,Spinal cord ,spinal cord injury ,0104 chemical sciences ,medicine.anatomical_structure ,chemistry ,lcsh:QD1-999 ,graphene oxide ,0210 nano-technology ,business ,Biomedical engineering - Abstract
Neural tissue engineering approaches show increasing promise for the treatment of neural diseases including spinal cord injury, for which an efficient therapy is still missing. Encouraged by both positive findings on the interaction of carbon nanomaterials such as graphene with neural components and the necessity of more efficient guidance structures for neural repair, we herein study the potential of reduced graphene oxide (rGO) microfibers as substrates for neural growth in the injured central neural tissue. Compact, bendable, and conductive fibers are obtained. When coated with neural adhesive molecules (poly-L-lysine and N-cadherin), these microfibers behave as supportive substrates of highly interconnected cultures composed of neurons and glial cells for up to 21 days. Synaptic contacts close to rGO are identified. Interestingly, the colonization by meningeal fibroblasts is dramatically hindered by N-cadherin coating. Finally, in vivo studies reveal the feasible implantation of these rGO microfibers as a guidance platform in the injured rat spinal cord, without evident signs of subacute local toxicity. These positive findings boost further investigation at longer implantation times to prove the utility of these substrates as components of advanced therapies for enhancing repair in the damaged central neural tissue including the injured spinal cord., This work was supported by the Instituto de Salud Carlos III-MINECO-FEDER (CP13/00060), the Ministerio de Economía y Competitividad, and the Fondo Europeo de Desarrollo Regional (MAT2016-78857-R and MAT2015-68639-R, MINECO/FEDER, UE). It was also partially funded by the European Union’s Horizon 2020 research and innovation programme under grant agreement No. 737116. more...
- Published
- 2017
9. Carbon–GO Composites with Preferential Water versus Ethanol Uptake
- Author
-
Aitana Tamayo, Francisco del Monte, M. Luisa Ferrer, Carlos Cuadrado-Collados, María C. Gutiérrez, Li-Zhi Guan, Julián Patiño, Joaquín Silvestre-Albero, Universidad de Alicante. Departamento de Química Inorgánica, Universidad de Alicante. Instituto Universitario de Materiales, and Materiales Avanzados more...
- Subjects
Deep eutectic solvent ,Polycondensation ,Química Inorgánica ,Condensation polymer ,Ethanol ,Materials science ,Water adsorption ,010405 organic chemistry ,Carbonization ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Carbon-GO composites ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,General Materials Science ,Carbon ,Graphene oxide - Abstract
The elimination of small amounts of water from alcohols is by no means a trivial issue in many practical applications like, for instance, the dehumidification of biocombustibles. The use of carbonaceous materials as sorbents has been far less explored than that of other materials because their hydrophobic character has typically limited their water uptake. Herein, we designed a synthetic process based on the use of eutectic mixtures that allowed the homogeneous dispersion of graphene oxide (GO) in the liquid containing the carbon precursor, e.g., furfuryl alcohol. Thus, after polymerization and a subsequent carbonization process, we were able to obtain porous carbon–GO composites where the combination of pore diameter and surface hydrophilicity provided a remarkable capacity for water uptake but extremely low methanol and ethanol uptake along the entire range of relative pressures evaluated in this work. Both the neat water uptake and the uptake difference between water and either methanol or ethanol of our carbon–GO composites were similar or eventually better than the uptake previously reported for other materials, also exhibiting preferential water-to-alcohol adsorption, e.g., porous coordination polymers, metal–organic frameworks, polyoxometalates, and covalent two-dimensional nanosheets embedded in a polymer matrix. Moreover, water versus alcohol uptake was particularly remarkable at low partial pressures in our carbon–GO composites. This work was supported by MINECO/FEDER (Project Numbers MAT2015-68639-R, MAT2016-80285-P, and RTI2018-097728-B-I00). L.Z.G. acknowledges the Chinese Scholarship Council for a PhD research fellowship (CSC No. 201608330266). C.C.-C. acknowledges UA for a research contract. more...
- Published
- 2019
10. Vortex ring processes allowing shape control and entrapment of antibacterial agents in GO-based particles
- Author
-
Luis Yuste, María C. Gutiérrez, M. Luisa Ferrer, Fernando Rojo, Li-Zhi Guan, Francisco del Monte, Ministerio de Economía y Competitividad (España), European Commission, and China Scholarship Council
- Subjects
Aqueous solution ,Materials science ,Drop (liquid) ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Vortex ring ,Suspension (chemistry) ,Drop impact ,Surface tension ,Antibacterial ,Membrane ,Chemical engineering ,GO particles ,Magnetic nanoparticles ,General Materials Science ,0210 nano-technology ,Vortex ring processes - Abstract
Vortex ring (VR) processes have proved highly effective in tailoring the morphology/shape of particles prepared from nanoclays, silica nanocolloids, magnetic nanoparticles and different polysaccharides. Herein, we have prepared toroidal-, teardrop-, jellyfish-, and cap-shaped vortex ring particles by drip- ping an aqueous suspension of graphene oxide (GO) into a cetyl trimethylammonium bromide (CTAB) aqueous solution that played the role of coagulating agent. Interestingly, the GO suspension exhibited liquid crystalline features. We demonstrated how controlling the drop impact force against the liquid surface was critical to produce VR particles with such intriguing shapes. With the purpose of controlling the drop impact force, we studied the drop density/viscosity, the speed at which the drop impacts the surface of the liquid pool and the surface tension of the CTAB solution. Finally, we also demonstrated the antibacterial activity of the resulting GO-based VR particles against Escherichia coli and Bacillus subtilis, and discussed about the origin of such a behaviour. In particular, we investigated the occurrence of (1) membrane damage by physical contact between GO and bacteria, (2) GO-induced oxidative stress, or (3) CTAB released into the bacteria culture, the antiseptic and disinfectant action of which may ultimately kill bacteria., This work was supported by MINECO/FEDER (Project Numbers MAT2015-68639-R and BIO2015-66203-P). L. Z. Guan also acknowledges Chinese Scholarship Council for a PhD research fellowship. more...
- Published
- 2019
11. Should deep eutectic solvents be treated as a mixture of two components or as a pseudo-component?
- Author
-
Francisco del Monte, Huan Zhang, María C. Gutiérrez, Xuejun Lu, M. Luisa Ferrer, and Laura González-Aguilera
- Subjects
Aqueous solution ,010304 chemical physics ,Serial dilution ,Component (thermodynamics) ,Analytical chemistry ,General Physics and Astronomy ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Viscosity ,chemistry.chemical_compound ,chemistry ,Molar ratio ,0103 physical sciences ,Urea ,Physical and Theoretical Chemistry ,Eutectic system ,Choline chloride - Abstract
Deep eutectic solvents (DESs) and dilutions thereof (mainly in H2O but also in many other non-aqueous solvents and co-solvent mixtures) have recently attracted great attention. It is well known that DES dilutions exhibit deviations from ideality. Interestingly, the treatment of DES as a mixture of two components or a pseudo-component is by no means trivial when determining deviations in density and, mainly, in viscosity. Herein, we studied aqueous dilutions of one of the most widely studied DES, this is, that composed of choline chloride and urea in a 1:2 molar ratio (e.g., ChCl2U). Using density and viscosity data reported in previous works, we calculated the excess molar volumes (VE) and excess viscosities (ln ηE) considering ChCl2U as either a mixture of two components or a pseudo-component, that is, taking the DES molecular weight as MChCl2U = fChClMChCl + fUMU = 86.58 g mol−1 (with fChCl = 1/3 and fU = 2/3) or as M*ChCl2U = MChCl + 2 MU = 259.74 g mol−1. We found that neither the sign of VE and VE* nor their evolution with temperature was influenced by the use of either MChCl2U or M*ChCl2U, and only the absolute magnitude of the deviation and the DES content (in wt. %) at which the minimum appears exhibited some differences. However, ln ηE and ln ηE* exhibited opposite signs, negative and positive, respectively. The odd achievement of negative ln ηE in aqueous dilutions of ChCl2U characterized by the formation of HB networks suggest the treatment of ChCl2U as a pseudo-component as more appropriate. Moreover, the role played by the presence of U in the evolution of ln ηE* with temperature was also discussed. more...
- Published
- 2021
- Full Text
- View/download PDF
12. Tools for extending the dilution range of the 'solvent-in-DES' regime
- Author
-
Huan Zhang, Rafael J. Jiménez-Riobóo, María C. Gutiérrez, Francisco del Monte, and M. Luisa Ferrer
- Subjects
Ethanol ,Serial dilution ,Analytical chemistry ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,01 natural sciences ,Atomic and Molecular Physics, and Optics ,0104 chemical sciences ,Electronic, Optical and Magnetic Materials ,Dilution ,Solvent ,chemistry.chemical_compound ,chemistry ,Materials Chemistry ,Methanol ,Physical and Theoretical Chemistry ,0210 nano-technology ,Ethylene glycol ,Spectroscopy ,Tetraethylammonium bromide ,Choline chloride - Abstract
Deep eutectic solvents (DESs) and dilutions thereof are currently gaining increased interest in sustainable processes. DES dilutions are particularly interesting in the so-called “solvent-in-DES” regime where the intriguing features of DESs remain (coming from hydrogen bonding among the components) and some typical drawbacks (e.g., high viscosity, low electrical conductivity, etc.) are mitigated. Actually, DES dilutions may exhibit excellent performances (more so than the original neat DESs) in certain applications. Knowing about the tools that allow predicting (and eventually extending) the dilution range of the “solvent-in-DES” regime is obviously of interest. With this aim, we herein studied two sets of DES dilutions. In the first set, we used the DES composed of choline chloride (ChCl) and urea (U) and its dilutions in H2O, methanol (MeOH) and ethanol (EtOH). In the second set, we studied two DESs composed of ethylene glycol (EG) and either tetraethylammonium bromide (TEABr) or tetrabutylammonium bromide (TBABr), and their dilutions in H2O. Data coming from DSC, 1H NMR spectroscopy, and Brillouin spectroscopy revealed how the dilution range of the “solvent-in-DES” regime in ChClU dilutions in H2O, MeOH and EtOH increased in the order H2O more...
- Published
- 2021
- Full Text
- View/download PDF
13. Encoding Metal-Cation Arrangements in Metal-Organic Frameworks for Programming the Composition of Electrocatalytically Active Multimetal Oxides
- Author
-
M. Angeles Monge, María C. Gutiérrez, Celia Castillo-Blas, Enrique Gutiérrez-Puebla, Inés Puente-Orench, Nieves López-Salas, M. Luisa Ferrer, Felipe Gándara, Ministerio de Economía y Competitividad (España), Ministerio de Ciencia, Innovación y Universidades (España), and Consejo Superior de Investigaciones Científicas (España) more...
- Subjects
Oxygen reduction ,Spinel oxides ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Multication metal-organic frameworks ,Catalysis ,law.invention ,Metal ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,law ,Oxygen reduction reaction ,Calcination ,General Chemistry ,0104 chemical sciences ,chemistry ,Chemical engineering ,visual_art ,visual_art.visual_art_medium ,Metal-organic framework ,Composition (visual arts) ,Methanol - Abstract
[EN] In the present contribution, we report how through the use of metal-organic frameworks (MOFs) composed of addressable combinations of up to four different metal elements it is possible to program the composition of multimetal oxides, which are not attainable by other synthetic methodologies. Thus, due to the ability to distribute multiple metal cations at specific locations in the MOF secondary building units it is possible to code and transfer selected metal ratios to multimetal oxides with novel, desired compositions through a simple calcination process. The demonstration of an enhancement in the electrocatalytic activity of new oxides by preadjusting the metal ratios is here reported for the oxygen reduction reaction, for which activity values comparable to commercial Pt/C catalysts are reached, while showing long stability and methanol tolerance., We acknowledge Institut Laue-Langevin and Spanish Initiatives on Neutron Scattering (ILL-SpINS) for beamtime at instrument D1B and G. Cuello for assistance during data acquisition. The Paul Scherrer Institute is also acknowledged for beamtime at instrument HRPT and V. Pomjakhusin for assistance during data acquisition. We thank E. Rodríguez-Cañas and Isidoro Poveda from the Servicio Interdepartamental de Investigación at Universidad Autónoma de Madrid for valuable support with SEM images and EDS analyses and FE-SEM image acquisition, respectively. We acknowledge E. Urones for the TEM images and TEM-EDS analysis acquisition at Centro Nacional de Microscopía Electrónica. Funding: Work at Instituto de Ciencia de Materiales de Madrid−Consejo Superior de Investigaciones Cientifícas (CSIC) has been supported by the Spanish Ministry for Science, Innovation and Universities (MINECO), and FEDER funds: Projects MAT2016-78465-R, MAT2015-68639-R, and CTQ2017-87262-R. F.G. and N.L.-S. acknowledge financial support from MINECO (Ramón y Cajal program and FPI research contract, respectively). more...
- Published
- 2019
14. Near-to-eutectic mixtures as bifunctional catalysts in the low-temperature-ring-opening-polymerization of ε-caprolactone
- Author
-
María C. Gutiérrez, Francisco del Monte, María Concepción Serrano, Carolina García, Sara García-Argüelles, M. Luisa Ferrer, Ministerio de Economía y Competitividad (España), Ministerio de Ciencia e Innovación (España), European Commission, and Instituto de Salud Carlos III more...
- Subjects
Acrylate ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Pollution ,Ring-opening polymerization ,Methanesulfonic acid ,0104 chemical sciences ,chemistry.chemical_compound ,Monomer ,Polymerization ,chemistry ,Polymer chemistry ,Copolymer ,Environmental Chemistry ,Organic chemistry ,0210 nano-technology ,Bifunctional ,Caprolactone - Abstract
We have investigated the ring-opening polymerization (ROP) of ε-caprolactone using mixtures of methanesulfonic acid and the guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene as the catalyst. Our interest in these mixtures is based on the capability of both acids and bases to behave as bifunctional catalysts; the former by the combined action of acidic hydrogens and basic oxygens, and the latter by the hydrogen-bond acceptor and donor features of, respectively, a basic nitrogen center and an ortho-hydrogen atom. We found that these compounds are capable of forming eutectic mixtures at a certain molar ratio. Upon the use of these mixtures – e.g. with molar ratios near to the eutectic one – as catalysts, neither further solvents nor initiators were required to carry out the ROP of ε-caprolactone. The resulting polycaprolactones (PCLs) were highly crystalline (more than 87%) and exhibited an excellent capability to support the growth of murine L929 fibroblasts. We consider that the preparation of biocompatible PCLs at physiological temperatures and in the absence of reagents other than the monomer and the catalyst offers an interesting alternative to both the self-cross-linked oligomers/macromers of acrylate-based PCL-derivatives and the pH/temperature-sensitive PCL copolymers used to date as injectable biomaterials., This work was supported by MINECO under grants MAT2012-34811 and MAT2011-25329, and by the European Union Seventh Framework Programme (FP7/2007-2013/NMP) under grant agreement #263289 (Green Nano Mesh). M.C.S. is grateful to the Instituto de Salud Carlos III-MINECO for a Miguel Servet type I contract. more...
- Published
- 2015
- Full Text
- View/download PDF
15. Highly Efficient and Recyclable Carbon‐Nanofiber‐Based Aerogels for Ionic Liquid–Water Separation and Ionic Liquid Dehydration in Flow‐Through Conditions
- Author
-
Francisco del Monte, Ricardo Jiménez, M. Luisa Ferrer, María C. Gutiérrez, Li-Zhi Guan, and María J. Roldán-Ruiz
- Subjects
Aqueous solution ,Materials science ,Carbon nanofiber ,Mechanical Engineering ,02 engineering and technology ,Liquid nitrogen ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Electrochemistry ,01 natural sciences ,0104 chemical sciences ,Catalysis ,law.invention ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,Mechanics of Materials ,law ,Ionic liquid ,General Materials Science ,Absorption (chemistry) ,0210 nano-technology ,Filtration - Abstract
Ionic liquids (ILs) are being widely used in many diverse areas of social interest, including catalysis, electrochemistry, etc. However, issues related to hygroscopicity of many ILs and the toxic and/or nonbiodegradable features of some of them limit their practical use. Developing materials capable of IL recovery from aqueous media and dehydration, thus allowing their recycling and subsequent reutilization, in a single and efficient process still poses a major challenge. Herein, electrically conductive aerogels composed of carbon nanofibers (CNFs) with remarkable superhydrophobic features are prepared. CNF-based 3D aerogels are prepared through a cryogenic process, so called ice-segregation-induced self-assembly (ISISA) consisting of the unidirectional immersion of an aqueous chitosan (CHI) solution also containing CNFs in suspension into a liquid nitrogen bath, and subsequent freeze-drying. The CNF-based 3D aerogels prove effective for absorption of ILs from aqueous biphasic systems and recovery with quite low water contents just through a single process of filtration. Moreover, the electrical conductivity of CNF-based 3D aerogels is particularly interesting to treat highly viscous ILs because the Joule effect allows not only shortening of the absorption process but also enhancement of the flux rate when operating in flow-through conditions. more...
- Published
- 2019
- Full Text
- View/download PDF
16. Efficient nitrogen-doping and structural control of hierarchical carbons using unconventional precursors in the form of deep eutectic solvents
- Author
-
Francisco del Monte, María C. Gutiérrez, M. Luisa Ferrer, José Luis García Fierro, Conchi O. Ania, Nieves López-Salas, Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), The City College of New York (CCNY), City University of New York [New York] (CUNY), Instituto Nacional del Carbon (INCAR), Instituto Nacional del Carbón, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Ministerio de Economía y Competitividad (España) more...
- Subjects
Condensation polymer ,[SDE.IE]Environmental Sciences/Environmental Engineering ,Renewable Energy, Sustainability and the Environment ,Carbonization ,chemistry.chemical_element ,[CHIM.CATA]Chemical Sciences/Catalysis ,[CHIM.MATE]Chemical Sciences/Material chemistry ,General Chemistry ,chemistry.chemical_compound ,chemistry ,Nucleophilic substitution ,Phenol ,Organic chemistry ,General Materials Science ,Melamine ,Carbon ,ComputingMilieux_MISCELLANEOUS ,Eutectic system ,Choline chloride - Abstract
Since the seminal work by Pekala in 1989, polycondensation of phenol derivatives with formaldehyde and subsequent carbonization has been one of the most used procedures for preparation of porous carbons. Nitrogen-doped carbons have also been obtained through this approach only by using nitrogen-rich precursors. The list of the most commonly used nitrogen-rich precursors includes melamine, urea, 3-hydroxypyridine, 3-aminophenol and lysine, and despite a few of them can be used in a single fashion, they typically need to be co-condensed with a second precursor. Nitrogen-rich precursors different from these ones have been used rarely because their molecular structure does not favor the nucleophilic substitution through which polycondensation takes place-e.g. p-nitrophenol. This is by no means a trivial issue because, on the one hand, these precursors cannot form a cross-linked network by themselves, and on the other hand, it may be difficult to encompass their different reaction kinetics when combined with more reactive precursors. This is also the situation for other precursors with an amphiphilic molecular structure that could be of interest to control the structure of the resulting porous carbons-e.g. 4-hexylresorcinol. In this work, we have used deep eutectic solvents composed of resorcinol, 4-hexylresorcinol, p-nitrophenol and choline chloride for the preparation of nitrogen-doped carbon monoliths with a hierarchical porous structure. Carbon conversions ranged from 64 to 50%-depending on the carbonization temperature-despite using three different carbon precursors for co-condensation and two of them were uncommon. The nitrogen content ranged from 4.9 to 3.0 wt%, revealing an excellent nitrogen-doping efficiency for p-nitrophenol when used in the form of DES. Finally, the use of 4-hexylresorcinol controlled the formation of a narrow microporosity that, in combination with the nitrogen functionalities, provided a remarkable CO2-sorption capability to the resulting carbons., This work was supported by the MINECO (MAT2012-34811 and MAT2011-25329). NLS acknowledges the MINECO for a FPI contract. more...
- Published
- 2014
- Full Text
- View/download PDF
17. Deep eutectic solvents as both active fillers and monomers for frontal polymerization
- Author
-
Francisco del Monte, Josué D. Mota-Morales, Gabriel Luna-Bárcenas, John A. Pojman, Isaac C. Sanchez, María C. Gutiérrez, M. Luisa Ferrer, and Eduardo A. Elizalde-Peña
- Subjects
chemistry.chemical_classification ,Polymers and Plastics ,Deep eutectic solvents ,Organic Chemistry ,Salt (chemistry) ,Active filler ,Polymer ,Drug delivery systems ,chemistry.chemical_compound ,Biopolymers ,Monomer ,chemistry ,Polymerization ,Polymer chemistry ,Materials Chemistry ,Ammonium ,Reactivity (chemistry) ,Frontal polymerizatio ,Cross-linking ,Eutectic system ,Acrylic acid - Abstract
The deep eutectic solvents (DESs) based on the mixtures of a variety of ammonium salts and hydrogen bond donors containing acrylic acids and acrylamides are capable of sustaining frontal polymerization (FP). The selection of ammonium salt affects the reactivity and allows FP at relatively low temperature but with full conversion. Also, full conversion allows us to use these polymers for biomedical applications (e.g., drug delivery systems) as the unreactive ammonium salts can be released from the resulting polymer without by-products. We call these components >active fillers,> which can be ammonium salts with biological or pharmaceutical importance. For instance, we prepared poly(acrylic acid) loaded with lidocaine hydrochloride (a common anesthetic), the release of which was found to occur in a controlled fashion. The ammonium salts also create a sufficiently high viscosity to suppress buoyancy-driven convection without additional materials. The DES here described played an all-in-one role, providing the monomer, the active filler, and the polymerization medium for FPs. © 2013 Wiley Periodicals, Inc., Funded by: CONACYT. Grant Number: 181678. more...
- Published
- 2013
- Full Text
- View/download PDF
18. Correction: Phosphorus-doped carbon–carbon nanotube hierarchical monoliths as true three-dimensional electrodes in supercapacitor cells
- Author
-
Julián Patiño, Nieves López-Salas, María C. Gutiérrez, Daniel Carriazo, M. Luisa Ferrer, and Francisco del Monte
- Subjects
Renewable Energy, Sustainability and the Environment ,Hardware_INTEGRATEDCIRCUITS ,General Materials Science ,Hardware_PERFORMANCEANDRELIABILITY ,General Chemistry ,Hardware_LOGICDESIGN - Abstract
Correction for ‘Phosphorus-doped carbon–carbon nanotube hierarchical monoliths as true three-dimensional electrodes in supercapacitor cells’ by Julián Patiño et al., J. Mater. Chem. A, 2016, 4, 1251–1263. more...
- Published
- 2018
- Full Text
- View/download PDF
19. Phosphate-Functionalized Carbon Monoliths from Deep Eutectic Solvents and their Use as Monolithic Electrodes in Supercapacitors
- Author
-
Francisco del Monte, Daniel Carriazo, José Luis García Fierro, Fernando Picó, María C. Gutiérrez, M. Luisa Ferrer, and José M. Rojo
- Subjects
Glycerol ,Materials science ,General Chemical Engineering ,Inorganic chemistry ,chemistry.chemical_element ,Electric Capacitance ,Electrochemistry ,Catalysis ,Phosphates ,chemistry.chemical_compound ,Chlorides ,Environmental Chemistry ,Phosphoric Acids ,General Materials Science ,Electrodes ,Eutectic system ,Supercapacitor ,Resorcinols ,Phosphate ,Carbon ,General Energy ,chemistry ,Chemical engineering ,Electrode ,Solvents ,Porous medium - Published
- 2012
- Full Text
- View/download PDF
20. Chitosan Gelation Induced by the in Situ Formation of Gold Nanoparticles and Its Processing into Macroporous Scaffolds
- Author
-
María J. Hortigüela, María C. Gutiérrez, Francisco del Monte, Inmaculada Aranaz, and M. Luisa Ferrer
- Subjects
Hot Temperature ,Polymers and Plastics ,Metal Nanoparticles ,Mineralogy ,Bioengineering ,Thermal treatment ,Catalysis ,Nitrophenols ,Biomaterials ,Chitosan ,chemistry.chemical_compound ,Materials Chemistry ,Fluorescence microscope ,medicine ,Dissolution ,Aqueous solution ,Hydrogels ,chemistry ,Chemical engineering ,Colloidal gold ,Self-healing hydrogels ,Gold ,Swelling ,medicine.symptom ,Oxidation-Reduction ,Porosity - Abstract
This work describes a simple synthetic route to induce chitosan (CHI) gelation by the in situ formation of gold nanoparticles (AuNPs). AuNPs were obtained by thermal treatment (e.g., 40 and 80 °C) of CHI aqueous solutions containing HAuCl(4) and in the absence of further reducing agents. The CHI hydrogels resulting after AuNP formation were submitted to unidirectional freezing and subsequent freeze-drying via ISISA (ice-segregation-induced self-assembly) process for the preparation of CHI scaffolds. The study of AuNP-CHI scaffolds by SEM and confocal fluorescence microscopy revealed a morphological structure characteristic of the hydrogel nature of the samples subjected to the ISISA process. Interestingly, not only the morphology but also the dissolution and swelling degree of the resulting CHI scaffolds were strongly influenced by the strength of the hydrogels obtained by the in situ formation of AuNP. We have also studied the catalytic activity AuNP-CHI scaffolds in the reduction of p-nitrophenol. The negligible dissolution and low swelling degree obtained in certain AuNP-CHI scaffolds allowed them to be used for more than four cycles with full preservation of the reaction kinetics. more...
- Published
- 2010
- Full Text
- View/download PDF
21. Resorcinol-Based Deep Eutectic Solvents as Both Carbonaceous Precursors and Templating Agents in the Synthesis of Hierarchical Porous Carbon Monoliths
- Author
-
M. Luisa Ferrer, Daniel Carriazo, María C. Gutiérrez, and Francisco del Monte
- Subjects
Materials science ,Carbonization ,General Chemical Engineering ,General Chemistry ,Resorcinol ,Freezing point ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,Ionic liquid ,Materials Chemistry ,Melting point ,Moiety ,Organic chemistry ,Mesoporous material ,Eutectic system - Abstract
Deep eutectic solvents are a new class of ionic liquids obtained via the complexion of quaternary ammonium salts with hydrogen-bond donors (such as acids, amines, and alcohols, among others). The charge delocalization that occurs through hydrogen bonding between the halide anion with the hydrogen-donor moiety is responsible for the decrease in the freezing point of the mixture, relative to the melting points of the individual components. We have recently reported on the use of deep eutectic solvents as suitable solvents, to carry out the polycondensation of resorcinol−formaldehyde. [Chem. Mater. 2010, 22, 2711−2719.] Herein, we describe the synthesis of deep eutectic solvents (DESs) based on resorcinol, the use of which as both carbonaceous precursors and structure-directing agents allowed the preparation of hierarchical porous (bimodal, with micropores and mesopores) carbon monoliths via formaldehyde polycondensation and subsequent carbonization. The performance of resorcinol-based DESs as carbonaceous p... more...
- Published
- 2010
- Full Text
- View/download PDF
22. Nitrogen-doped carbons prepared from eutectic mixtures as metal-free oxygen reduction catalysts
- Author
-
Francisco del Monte, M. Luisa Ferrer, María C. Gutiérrez, Nieves López-Salas, Miguel A. Muñoz-Márquez, Conchi O. Ania, Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), The City College of New York (CCNY), City University of New York [New York] (CUNY), Instituto Nacional del Carbon (INCAR), Instituto Nacional del Carbón, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), and Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) more...
- Subjects
Materials science ,Inorganic chemistry ,chemistry.chemical_element ,02 engineering and technology ,Resorcinol ,010402 general chemistry ,Molecular sieve ,01 natural sciences ,Catalysis ,chemistry.chemical_compound ,General Materials Science ,ComputingMilieux_MISCELLANEOUS ,Eutectic system ,Renewable Energy, Sustainability and the Environment ,Carbonization ,[SDE.IE]Environmental Sciences/Environmental Engineering ,General Chemistry ,[CHIM.CATA]Chemical Sciences/Catalysis ,[CHIM.MATE]Chemical Sciences/Material chemistry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,3. Good health ,chemistry ,0210 nano-technology ,Selectivity ,Platinum ,Choline chloride - Abstract
Deep eutectic solvents (DESs) composed of resorcinol, either 2-cyanophenol or 4-cyanophenol, and choline chloride were used for the synthesis of hierarchical nitrogen-doped carbon molecular sieves. Carbons were obtained with high conversions by polycondensation of resorcinol and either 2-cyanophenol or 4-cyanophenol with formaldehyde, and subsequent carbonization at 800 °C in nitrogen atmosphere. The nitrogen content was ca. 2.4 wt%, revealing an excellent nitrogen-doping efficiency for cyanophenol derivatives when used in the form of DES. The use of either 2-cyanophenol or 4-cyanophenol modified the contribution of quaternary-Nvalley groups in the resulting carbons, being larger in carbons coming from 4-cyanophenol than in those coming from 2-cyanophenol. The hierarchical porous structure was composed of micro-, meso- and macropores, and the diameter distribution of mesopores was also related to the use of either 2-cyanophenol or 4-cyanophenol. These structural and compositional differences were critical for the use of the resulting hierarchical nitrogen-doped carbons as efficient metal-free electrocatalysts. In particular, the carbons coming 4-cyanophenol proved particularly effective in the direct reduction of oxygen to OH− (H2O in acidic solution) through a four-electron (4e−) process with high catalytic activity and selectivity, and longer stability and stronger tolerance to crossover effects than platinum-based electrocatalysts. more...
- Published
- 2016
- Full Text
- View/download PDF
23. Phosphorus-doped carbon-carbon nanotube hierarchical monoliths as true three-dimensional electrodes in supercapacitor cells
- Author
-
Nieves López-Salas, Francisco del Monte, M. Luisa Ferrer, Julián Patiño, María C. Gutiérrez, Daniel Carriazo, and Ministerio de Economía y Competitividad (España)
- Subjects
Supercapacitor ,Nanotube ,Triethyl phosphate ,Materials science ,Renewable Energy, Sustainability and the Environment ,Carbonization ,02 engineering and technology ,General Chemistry ,Current collector ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Furfuryl alcohol ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,Electrode ,Surface modification ,General Materials Science ,Composite material ,0210 nano-technology - Abstract
Eutectic mixtures of the monohydrated form of p-toluenesulfonic acid (pTsOH·HO) and triethyl phosphate (TEP) in a 1: 1 molar ratio were used as the medium to disperse previously functionalized multiwalled carbon nanotubes (MWCNTs), and to catalyse the polycondensation of furfuryl alcohol. Hierarchically structured P-doped carbon-CNT composites were obtained after carbonization. The high surface area, the phosphate functionalization, the hierarchical structure and the good electrical conductivity exhibited by these composites provided remarkable metrics when they were used as electrodes in a supercapacitor cell, with energy densities of around 22.6 W h kg and power densities of up to 10 kW kg for operational voltages of up to 1.5 V. This performance surpasses any performance previously reported for electrodes weighing (at least) 10 mg per cm of current collector and using an aqueous electrolyte. Actually, the supercapacitor cell built up with these electrodes provided enough neat energy to turn an IR LED of 30 mW on and emit light over a certain period., This study was supported by MINECO (MAT2012-34811). J. P. and N. L.-S. acknowledge MINECO for their respective FPI contracts. more...
- Published
- 2016
24. Correction: Nitrogen-doped carbons prepared from eutectic mixtures as metal-free oxygen reduction catalysts
- Author
-
Francisco del Monte, Miguel A. Muñoz-Márquez, Conchi O. Ania, M. Luisa Ferrer, María C. Gutiérrez, and Nieves López-Salas
- Subjects
Materials science ,Metal free ,Renewable Energy, Sustainability and the Environment ,Inorganic chemistry ,Hardware_INTEGRATEDCIRCUITS ,General Materials Science ,Nitrogen doped ,General Chemistry ,Oxygen reduction ,Catalysis ,Eutectic system - Abstract
Correction for ‘Nitrogen-doped carbons prepared from eutectic mixtures as metal-free oxygen reduction catalysts’ by Nieves López-Salas et al., J. Mater. Chem. A, 2016, 4, 478–488.
- Published
- 2018
- Full Text
- View/download PDF
25. Synthesis of novel lidocaine-releasing poly(diol-co-citrate) elastomers by using deep eutectic solvents
- Author
-
Francisco del Monte, María C. Gutiérrez, Ricardo Jiménez, M. Concepción Serrano, and M. Luisa Ferrer
- Subjects
Hot Temperature ,Materials science ,Lidocaine ,Polymers ,Diol ,Chemistry Techniques, Synthetic ,Elastomer ,Catalysis ,chemistry.chemical_compound ,Polymer chemistry ,Materials Chemistry ,medicine ,Citrates ,Anesthetics, Local ,Eutectic system ,Drug Carriers ,Metals and Alloys ,High loading ,General Chemistry ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Elastomers ,Chemical engineering ,chemistry ,Solvents ,Ceramics and Composites ,medicine.drug - Abstract
Poly(octanediol-co-citrate) elastomers containing high loading of lidocaine were synthesized at temperatures below 100 °C by means of using deep eutectic mixtures of 1,8-octanediol and lidocaine. The preservation of lidocaine integrity resulted in high-capacity drug-eluting elastomers. more...
- Published
- 2012
- Full Text
- View/download PDF
26. Mammalian cell cryopreservation by using liquid marbles
- Author
-
María C. Gutiérrez, Francisco del Monte, M. Concepción Serrano, M. Luisa Ferrer, and Stefania Nardecchia
- Subjects
Polymers ,Surface Properties ,Cell ,Liquid marble ,Nanotechnology ,Cryopreservation ,Cell Line ,Flow cytometry ,Mice ,Mammalian cell ,medicine ,Animals ,General Materials Science ,Particle Size ,Cytotoxicity ,Cell Proliferation ,medicine.diagnostic_test ,Chemistry ,Adhesion ,Fibroblasts ,Cell cycle ,medicine.anatomical_structure ,Microreactor ,PTFE ,Hydrophobic and Hydrophilic Interactions ,L929 fibroblast - Abstract
Liquid marbles (LMs) are nonsticky droplets covered by micro- or nanometrically scaled particles and obtained by simply rolling small amounts of a liquid in a very hydrophobic powder. Since pioneer work by Aussillous and Quéré, a wide palette of hydrophobic materials for the preparation of LMs, as well as potential applications, have been reported. Because of the bioinspired origin of this concept, the applicability of LMs in biomedicine is gaining increasing attention, with remarkable advances in their use as microbioreactors for blood typing, drug screening, and tumor growth, among others. Herein, we explore the novel use of LMs as a biotechnological tool for the cryopreservation of mammalian cells as an alternative to conventional methods, which typically require the use of cryopreservant agents that commonly associate with some degree of cell toxicity. Murine L929 fibroblasts, a reference cell line for cytotoxicity studies, and poly(tetrafluoroethylene), a hydrophobic polymer widely used in cardiovascular surgery, were selected for the preparation of the cell-containing LMs. Our results reveal that there is a safe range of droplet volumes and cell densities that can be successfully used to cryopreserve mammalian cell lines and recover them after thawing without significantly affecting major cellular parameters such as adhesion, morphology, viability, proliferation, and cell cycle. We envision that progress in the exploration of cell-containing LMs could also open their impact as microreactors for the miniaturization of cytotoxicity procedures of drugs and materials in which powerful tools for cell evaluation such as flow cytometry could be used because of the elevated amount of cells handled. more...
- Published
- 2015
27. Deep Eutectic Solvents Playing Multiple Roles in the Synthesis of Porous Carbon Materials
- Author
-
Francisco del Monte, María Concepción Serrano, Daniel Carriazo, M. Luisa Ferrer, and María C. Gutiérrez
- Subjects
Supercapacitor ,chemistry.chemical_compound ,Porous carbon ,Materials science ,Nanocomposite ,Phosphorus doped ,chemistry ,Chemical engineering ,Ionic liquid ,Electrode ,Inorganic chemistry ,Co2 adsorption ,Eutectic system - Abstract
This chapter discusses the use of deep eutectic solvent-assisted syntheses which allow the preparation of both chemically and structurally modified carbon monoliths suitable as electrodes in supercapacitor cells. Either carbons or carbon–carbon nanocomposites exhibiting a hierarchical structure and a tailored composition (either nitrogen or phosphorus doped) could be attained by the use of different mixtures of deep eutectic solvents (DESs). Carbons prepared from DESs are also suitable for CO2 adsorption and CO2–N2 and/or CO2–CH4 separation processes. These features, besides the low-cost character of our carbons, open interesting perspectives for their application as sorbents in separation technologies for CO2 low-pressure post-combustion processes and natural gas upgrading. more...
- Published
- 2015
- Full Text
- View/download PDF
28. Sulfur-doped carbons prepared from eutectic mixtures containing hydroxymethylthiophene as metal-free oxygen reduction catalysts
- Author
-
Francisco del Monte, José Luis García Fierro, Nieves López-Salas, Aitana Tamayo, M. Luisa Ferrer, Antonio L. De Lacey, María C. Gutiérrez, and Ministerio de Economía y Competitividad (España)
- Subjects
Magnetic Resonance Spectroscopy ,General Chemical Engineering ,Inorganic chemistry ,chemistry.chemical_element ,Thiophenes ,Complex Mixtures ,Heterogeneous catalysis ,Oxygen ,Catalysis ,Oxygen reduction reaction ,Furfuryl alcohol ,chemistry.chemical_compound ,Spectroscopy, Fourier Transform Infrared ,Environmental Chemistry ,General Materials Science ,Fuel cells ,Eutectic system ,Carbonization ,Sulfur ,Carbon ,General Energy ,chemistry ,Microscopy, Electron, Scanning ,Methanol ,Oxidation-Reduction ,Nuclear chemistry - Abstract
A template‐free approach based on the use of eutectic mixtures composed of 2‐hydroxymethylthiophene and furfuryl alcohol has been designed for the preparation of hierarchical sulfur‐doped carbons (SPCs) in monolithic form. The temperature used for carbonization, for example, 600, 800, or 900 °C, determined most of the physicochemical properties of the resulting SPCs. Thus, the surface area increased from below 400 to up 775 m2 g−1, along with the carbonization temperature, whereas the sulfur content decreased from approximately 15 to 5 wt %. The oxygen reduction reaction performance in samples carbonized at 900 °C was good, with the four‐electron‐transfer reaction prevailing over the two‐electron‐transfer one. Interestingly, the methanol tolerance and stability of these SPCs were also remarkable, with less than 5 % current decrease immediately after methanol addition, whereas, in terms of stability, the current decrease was below 8 % after 20000 s. This performance was in the range of that found not only for other SPCs, but also for many nitrogen‐doped and even some dual‐doped (S and N) ones., This work was supported by MINECO (MAT2012‐34811 and MAT2011‐25329). N.L.S. acknowledges MINECO for a FPI contract. more...
- Published
- 2014
29. ChemInform Abstract: Deep Eutectic Solvents in Polymerizations: A Greener Alternative to Conventional Syntheses
- Author
-
María Concepción Serrano, M. Luisa Ferrer, Francisco del Monte, Daniel Carriazo, and María C. Gutiérrez
- Subjects
Green chemistry ,Reaction conditions ,Polymerization ,Chemistry ,Reagent ,Radical polymerization ,Nanotechnology ,General Medicine ,Biocompatible material ,Eutectic system - Abstract
The use of deep eutectic solvents (DESs) that act as all-in-one solvent-template-reactant systems offers an interesting green alternative to conventional syntheses in materials science. This Review aims to provide a comprehensive overview to emphasize the similarities and discrepancies between DES-assisted and conventional syntheses and rationalize certain green features that are common for the three DES-assisted syntheses described herein: one case of radical polymerization and two cases of polycondensations. For instance, DESs contain the precursor itself and some additional components that either provide certain functionality (e.g., drug delivery and controlled release, or electrical conductivity) to the resulting materials or direct their formation with a particular structure (e.g., hierarchical-type). Moreover, DESs provide a reaction medium, so polymerizations are ultimately carried out in a solventless fashion. This means that DES-assisted syntheses match green chemistry principles 2 and 5 because of the economy of reagents and solvents, whereas the functionality incorporated by the second component allows the need for any post-synthesis derivatization to be minimized or even fully avoided (principle 8). DESs also provide new precursors that favor more efficient polymerization (principle 6) by decreasing the energy input required for reaction progress. Finally, the use of mild reaction conditions in combination with the compositional versatility of DESs, which allows low-toxic components to be selected, is also of interest from the viewpoint of green chemistry because it opens up the way to design biocompatible and/or eco-friendly synthetic methods (principle 3). more...
- Published
- 2014
- Full Text
- View/download PDF
30. Deep eutectic solvents in polymerizations: A greener alternative to conventional syntheses
- Author
-
María Concepción Serrano, M. Luisa Ferrer, Daniel Carriazo, Francisco del Monte, and María C. Gutiérrez
- Subjects
Green chemistry ,Green Chemistry Technology ,Chemistry ,General Chemical Engineering ,Radical polymerization ,Nanotechnology ,Eutectic solvents ,Chemistry Techniques, Synthetic ,Biocompatible material ,Materials science ,Polymerization ,Ionic liquids ,chemistry.chemical_compound ,General Energy ,Reagent ,Ionic liquid ,Environmental Chemistry ,General Materials Science ,Eutectic system - Abstract
The use of deep eutectic solvents (DESs) that act as all-in-one solvent-template-reactant systems offers an interesting green alternative to conventional syntheses in materials science. This Review aims to provide a comprehensive overview to emphasize the similarities and discrepancies between DES-assisted and conventional syntheses and rationalize certain green features that are common for the three DES-assisted syntheses described herein: one case of radical polymerization and two cases of polycondensations. For instance, DESs contain the precursor itself and some additional components that either provide certain functionality (e.g., drug delivery and controlled release, or electrical conductivity) to the resulting materials or direct their formation with a particular structure (e.g., hierarchical-type). Moreover, DESs provide a reaction medium, so polymerizations are ultimately carried out in a solventless fashion. This means that DES-assisted syntheses match green chemistry principles 2 and 5 because of the economy of reagents and solvents, whereas the functionality incorporated by the second component allows the need for any post-synthesis derivatization to be minimized or even fully avoided (principle 8). DESs also provide new precursors that favor more efficient polymerization (principle 6) by decreasing the energy input required for reaction progress. Finally, the use of mild reaction conditions in combination with the compositional versatility of DESs, which allows low-toxic components to be selected, is also of interest from the viewpoint of green chemistry because it opens up the way to design biocompatible and/or eco-friendly synthetic methods (principle 3). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim., MINECO. Grant Numbers: MAT2009-10214, MAT2011-25329, MAT2012-34811. more...
- Published
- 2014
31. ChemInform Abstract: Three Dimensional Macroporous Architectures and Aerogels Built of Carbon Nanotubes and/or Graphene: Synthesis and Applications
- Author
-
Francisco del Monte, M. Luisa Ferrer, María C. Gutiérrez, Stefania Nardecchia, and Daniel Carriazo
- Subjects
Mass transport ,Chemistry ,Graphene ,chemistry.chemical_element ,Nanotechnology ,General Medicine ,Carbon nanotube ,law.invention ,law ,Photocatalysis ,Electronics ,Thin film ,Performance enhancement ,Carbon - Abstract
Carbon nanotubes and graphene are some of the most intensively explored carbon allotropes in materials science. This interest mainly resides in their unique properties with electrical conductivities as high as 104 S cm−1, thermal conductivities as high as 5000 W m−1 K and superior mechanical properties with elastic moduli on the order of 1 TPa for both of them. The possibility to translate the individual properties of these monodimensional (e.g. carbon nanotubes) and bidimensional (e.g. graphene) building units into two-dimensional free-standing thick and thin films has paved the way for using these allotropes in a number of applications (including photocatalysis, electrochemistry, electronics and optoelectronics, among others) as well as for the preparation of biological and chemical sensors. More recently and while recognizing the tremendous interest of these two-dimensional structures, researchers are noticing that the performance of certain devices can experience a significant enhancement by the use of three-dimensional architectures and/or aerogels because of the increase of active material per projected area. This is obviously the case as long as the nanometre-sized building units remain accessible so that the concept of hierarchical three-dimensional organization is critical to guarantee the mass transport and, as consequence, performance enhancement. Thus, this review aims to describe the different synthetic processes used for preparation of these three-dimensional architectures and/or aerogels containing either any or both allotropes, and the different fields of application in which the particular structure of these materials provided a significant enhancement in the efficacy as compared to their two-dimensional analogues or even opened the path to novel applications. The unprecedented compilation of information from both CNT- and graphene-based three-dimensional architectures and/or aerogels in a single revision is also of interest because it allows a straightforward comparison between the particular features provided by each allotrope. more...
- Published
- 2013
- Full Text
- View/download PDF
32. Deep-eutectic-assisted synthesis of bimodal porous carbon monoliths with high electrical conductivities
- Author
-
Francisco del Monte, Daniel Carriazo, María C. Gutiérrez, Ricardo Jiménez, and M. Luisa Ferrer
- Subjects
Materials science ,Porous carbon ,Chemical engineering ,General Materials Science ,General Chemistry ,Condensed Matter Physics ,Eutectic system - Abstract
Hierarchically structured graphitic carbons synthesized from deep eutectic solvents exhibit a bicontinuous structure where the continuity of the graphitic domains throughout the entire 3D carbon network provides electrical conductivities of up to 31 S/cm to the depicted monoliths. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim., Funded by: MINECO. Grant Numbers: MAT2009–10214, MAT2011–25329, MAT2012–34811. more...
- Published
- 2013
33. Synthesis of macroporous poly(acrylic acid)-carbon nanotube composites by frontal polymerization in deep-eutectic solvents
- Author
-
Isaac C. Sanchez, Gabriel Luna-Bárcenas, Ricardo Jiménez, Mauricio Terrones, M. Luisa Ferrer, Josué D. Mota-Morales, Francisco del Monte, María C. Gutiérrez, and P. Santiago
- Subjects
Materials science ,Biocompatibility ,Renewable Energy, Sustainability and the Environment ,General Chemistry ,Solvent ,chemistry.chemical_compound ,Monomer ,chemistry ,Polymerization ,Methacrylic acid ,Polymer chemistry ,Ionic liquid ,General Materials Science ,Composite material ,Acrylic acid ,Choline chloride - Abstract
Deep Eutectic Solvents (DESs) formed between Acrylic Acid (AA) and Choline Chloride (CCl) exhibit certain properties of ionic liquids (e.g. high viscosity) that make them suitable for frontal polymerization (FP). The use of DESs not only as a monomer but also as the solvent prevents the use of additional solvents (i.e. typically of organic nature) and offers a green tool for the synthesis of functional composites. We have recently explored this approach for the preparation of poly(acrylic acid) (PAA) and poly(methacrylic acid). In this work, we have taken advantage of the outstanding capability of DESs to solubilize and/or disperse a number of substances to incorporate-in a homogeneous fashion-carbon nanotubes (in this particular case, N-doped MWCNT-CNxMWCNTs) in the polymerizable DES. Interestingly, CNxMWCNTs also played the role of an inert filler in FP. The resulting PAA-CNxMWCNT composites exhibited some distinct features as compared to previous PAA also obtained via DES-assisted FP. For instance, PAA-CNxMWCNT composites can undergo swelling depending on the pH, as bare PAA. However, the presence of CNxMWCNTs allows the formation of a macroporous structure after submission to a freeze-drying process, the achievement of which was not possible in bare PAA. The combination of structural (e.g. macroporosity) and functional (e.g. stimuli responsive) properties exhibited by these materials besides an eventually high biocompatibility-coming from the green character of the DES-assisted synthesis-should make the resulting macroporous PAA-CNxMWCNT composites excellent candidates for their future application as biomaterials. © 2013 The Royal Society of Chemistry., F. dM. acknowledges support from Grant reference numbers MAT2009-10214, MAT2011-25329,MAT2012-34811. P. Santiago acknowledges financial support from DGAPA-UNAM, through grant IN113411. more...
- Published
- 2013
34. Deep eutectic solvent-assisted synthesis of biodegradable polyesters with antibacterial properties
- Author
-
Francisco del Monte, M. Luisa Ferrer, Fernando Rojo, María C. Gutiérrez, Luis Yuste, M. Concepción Serrano, and Sara García-Argüelles
- Subjects
Polyesters ,Nanotechnology ,Context (language use) ,Biocompatible Materials ,Chemistry Techniques, Synthetic ,Microbial Sensitivity Tests ,Cell Line ,chemistry.chemical_compound ,Mice ,Organophosphorus Compounds ,Bromide ,Electrochemistry ,Escherichia coli ,Animals ,General Materials Science ,Phosphonium ,Spectroscopy ,chemistry.chemical_classification ,Surfaces and Interfaces ,Polymer ,Condensed Matter Physics ,Combinatorial chemistry ,Deep eutectic solvent ,Anti-Bacterial Agents ,Polyester ,Quaternary Ammonium Compounds ,chemistry ,Solvents ,Tetraethylammonium bromide ,Choline chloride - Abstract
Bacterial infection related to the implantation of medical devices represents a serious clinical complication, with dramatic consequences for many patients. In past decades, numerous attempts have been made to develop materials with antibacterial and/or antifouling properties by the incorporation of antibiotic and/or antiseptic compounds. In this context, deep eutectic solvents (DESs) are acquiring increasing interest not only as efficient carriers of active principle ingredients (APIs) but also as assistant platforms for the synthesis of a wide repertoire of polymer-related materials. Herein, we have successfully prepared biodegradable poly(octanediol-co-citrate) polyesters with acquired antibacterial properties by the DES-assisted incorporation of quaternary ammonium or phosphonium salts into the polymer network. In the resulting polymers, the presence of these salts (i.e., choline chloride, tetraethylammonium bromide, hexadecyltrimethylammonium bromide, and methyltriphenylphosphonium bromide) inhibits bacterial growth in the early postimplantation steps, as tested in cultures of Escherichia coli on solid agar plates. Later, positive polymer cytocompatibility is expected to support cell colonization, as anticipated from in vitro preliminary studies with L929 fibroblasts. Finally, the attractive elastic properties of these polyesters permit matching those of soft tissues such as skin. For all of these reasons, we envisage the utility of some of these antibacterial, biocompatible, and biodegradable polyesters as potential candidates for the preparation of antimicrobial wound dressings. These results further emphasize the enormous versatility of DES-assisted synthesis for the incorporation, in the synthesis step, of a wide palette of APIs into polymeric networks suitable for biomedical applications. © 2013 American Chemical Society., M.C.S. is greatly indebted to MINECO for a Juan de la Cierva fellowship. M. T. Portolés (Department of Biochemistry and Molecular Biology I, Universidad Complutense de Madrid) is acknowledged for generous supplying L929 fibroblasts. This work was supported by MINECO (grant reference numbers MAT2009-10214, MAT2011-25329, MAT2012-34811, and BFU2012-32797). more...
- Published
- 2013
35. Three dimensional macroporous architectures and aerogels built of carbon nanotubes and/or graphene: synthesis and applications
- Author
-
María C. Gutiérrez, Francisco del Monte, M. Luisa Ferrer, Stefania Nardecchia, and Daniel Carriazo
- Subjects
Models, Molecular ,Materials science ,Graphene ,Nanotubes, Carbon ,chemistry.chemical_element ,Nanotechnology ,General Chemistry ,Carbon nanotube ,law.invention ,chemistry ,law ,Photocatalysis ,Graphite ,Electronics ,Thin film ,Performance enhancement ,Porosity ,Carbon ,Gels - Abstract
Carbon nanotubes and graphene are some of the most intensively explored carbon allotropes in materials science. This interest mainly resides in their unique properties with electrical conductivities as high as 104 S cm-1, thermal conductivities as high as 5000 W m-1 K and superior mechanical properties with elastic moduli on the order of 1 TPa for both of them. The possibility to translate the individual properties of these monodimensional (e.g. carbon nanotubes) and bidimensional (e.g. graphene) building units into two-dimensional free-standing thick and thin films has paved the way for using these allotropes in a number of applications (including photocatalysis, electrochemistry, electronics and optoelectronics, among others) as well as for the preparation of biological and chemical sensors. More recently and while recognizing the tremendous interest of these two-dimensional structures, researchers are noticing that the performance of certain devices can experience a significant enhancement by the use of three-dimensional architectures and/or aerogels because of the increase of active material per projected area. This is obviously the case as long as the nanometre-sized building units remain accessible so that the concept of hierarchical three-dimensional organization is critical to guarantee the mass transport and, as consequence, performance enhancement. Thus, this review aims to describe the different synthetic processes used for preparation of these three-dimensional architectures and/or aerogels containing either any or both allotropes, and the different fields of application in which the particular structure of these materials provided a significant enhancement in the efficacy as compared to their two-dimensional analogues or even opened the path to novel applications. The unprecedented compilation of information from both CNT- and graphene-based three-dimensional architectures and/or aerogels in a single revision is also of interest because it allows a straightforward comparison between the particular features provided by each allotrope. © The Royal Society of Chemistry 2013., This work was supported by MINECO (projects MAT2012-34811, MAT2011-25329 and MAT2009-10214). more...
- Published
- 2013
36. Thermal unfolding and refolding of lysozyme in deep eutectic solvents and their aqueous dilutions
- Author
-
C. Reyes Mateo, Rocío Esquembre, Francisco del Monte, J. Gerard Wall, Jesús Sanz, and M. Luisa Ferrer
- Subjects
hen lysozyme ,Protein Folding ,Serial dilution ,Inorganic chemistry ,enzymes ,General Physics and Astronomy ,anhydrous organic-solvents ,equilibrium ,ionic liquids ,chemistry.chemical_compound ,intermediate ,Denaturation (biochemistry) ,Physical and Theoretical Chemistry ,Eutectic system ,Aqueous solution ,Chromatography ,Temperature ,Water ,stability ,Dilution ,biotransformations ,chemistry ,Solvents ,Urea ,Muramidase ,fluorescence ,Lysozyme ,protein ,Choline chloride - Abstract
The stability of hen's egg white lysozyme in different choline chloride-based pseudo-concentrated and neat deep eutectic solvents (DESs) has been studied by means of intrinsic fluorescence and CD spectroscopy. Thermal unfolding experiments carried out in non-diluted urea:choline chloride and glycerol:choline chloride eutectic solvents (UCCl-DES and GCCl-DES, respectively) showed the accumulation at certain temperatures of discrete, partially folded intermediates that displayed a high content of secondary structure and a disrupted tertiary structure. Reversibility of the unfolding process was incomplete in these circumstances, with the urea-based DES showing higher protein structure destabilization upon thermal treatment. On the other hand, aqueous dilution of the eutectic mixtures allowed the recovery of a reversible, two-state denaturation process. Lysozyme activity was also affected in neat and pseudo-concentrated GCCl-DES, with an increasing recovery of activity upon aqueous dilution, and full restoration after DES removal through extensive dialysis. These results suggest that protein interactions at room temperature are reversible and depend on the DES components and on the aqueous content of the original DES dilution. © 2013 the Owner Societies., This work was supported by grants MAT2009-10214, MAT2012-34811, MAT2008-05670 and BFU2010-17824 from the Spanish Ministry of Economy and Competitiveness. R. Esquembre acknowledges a predoctoral fellowship (BES-2006-12514) from MINECO. F. del Monte acknowledges a travel grant (PA1003268) from CSIC. more...
- Published
- 2013
37. Microwave-assisted synthesis of NiCo2O4-graphene oxide nanocomposites suitable as electrodes for supercapacitors
- Author
-
Francisco del Monte, Julián Patiño, María C. Gutiérrez, Daniel Carriazo, and M. Luisa Ferrer
- Subjects
Supercapacitor ,Materials science ,Nanocomposite ,Graphene ,General Chemical Engineering ,Nanowire ,Oxide ,Nanoparticle ,Nanotechnology ,General Chemistry ,Capacitance ,law.invention ,chemistry.chemical_compound ,chemistry ,law ,Pseudocapacitor - Abstract
Microwave irradiation combined with mild heating was demonstrated as a suitable synthetic method for the preparation of NiCo2O4 nanowires and NiCo2O4-graphene oxide nanocomposites. In both cases, the synthesis was carried out in just a few minutes, at relatively low temperatures and with a certain economy of reagents. In the particular case of the nanocomposites, NiCo2O4 was deposited in form of not only nanowires, but also ultrafine nanoparticles on the surface of graphene oxide sheets due to the preferred activation of these sheets under microwave irradiation. The nanocomposites exhibited a superior performance to NiCo 2O4 nanowires as electrodes in pseudocapacitors with capacitance retentions of nearly 735 F g-1 at current densities of up to 33 A g-1. © 2013 The Royal Society of Chemistry. more...
- Published
- 2013
38. Deep eutectic assisted synthesis of carbon adsorbents highly suitable for low-pressure separation of CO2–CH4 gas mixtures
- Author
-
Francisco del Monte, María C. Gutiérrez, José B. Parra, Julián Patiño, M. Luisa Ferrer, Daniel Carriazo, Conchi O. Ania, Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), The City College of New York (CCNY), City University of New York [New York] (CUNY), Instituto Nacional del Carbon (INCAR), Instituto Nacional del Carbón, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto Nacional del Carbon, and CSIC-Oviedo more...
- Subjects
Materials science ,Inorganic chemistry ,chemistry.chemical_element ,02 engineering and technology ,010402 general chemistry ,Molecular sieve ,01 natural sciences ,chemistry.chemical_compound ,Adsorption ,Environmental Chemistry ,ComputingMilieux_MISCELLANEOUS ,Eutectic system ,Renewable Energy, Sustainability and the Environment ,Hydrogen bond ,[SDE.IE]Environmental Sciences/Environmental Engineering ,[CHIM.CATA]Chemical Sciences/Catalysis ,[CHIM.MATE]Chemical Sciences/Material chemistry ,021001 nanoscience & nanotechnology ,Pollution ,0104 chemical sciences ,Nuclear Energy and Engineering ,chemistry ,Ionic liquid ,0210 nano-technology ,Mesoporous material ,Carbon ,Tetraethylammonium bromide - Abstract
Ionic liquids and deep eutectic solvents (a new class of ionic liquids obtained by complexation of quaternary ammonium salts with hydrogen bond donors such as acids, amines, and alcohols among others) have been recently used as solvents and even as precursors in the synthesis of carbonaceous materials. The use of long-alkyl-chain derivatives of ionic liquids that, playing the role of structure directing agents, were capable of designing the mesoporous structure of the resulting carbons is of particular interest. Meanwhile, deep eutectic solvents proved efficient in tailoring the structure comprised between large mesopores and small macropores, but the control over the smaller ones (e.g. small mesopores and micropores) is still a challenge as compared to ILs. Herein, we have used deep eutectic solvents composed of resorcinol, 4-hexylresorcinol and tetraethylammonium bromide for the synthesis of carbon monoliths with a tailor-made narrow microporosity. Behaving as molecular sieves, these carbons exhibited not only good capacities for CO2 adsorption (up to 3 mmol g−1) but also an outstanding – especially at low pressures – CO2–CH4 selectivity., This work was supported by MINECO (MAT2009‐10214 and MAT2011‐25329). DC acknowledges MINECO for a JdelaC research contract. JP acknowledges MINECO for a FPI fellowship. COA and JBP thank the financial support of FICYT (EQUIP08‐36, file num. 04010208000281). more...
- Published
- 2012
- Full Text
- View/download PDF
39. Phase behavior of elastin-like synthetic recombinamers in deep eutectic solvents
- Author
-
J. Carlos Rodríguez-Cabello, María C. Gutiérrez, Francisco del Monte, Isabel Miguel López, Stefania Nardecchia, Matilde Alonso, and M. Luisa Ferrer
- Subjects
Materials science ,Polymers and Plastics ,Bioengineering ,Structural water ,Phase Transition ,Choline ,Biomaterials ,Phase (matter) ,Materials Chemistry ,Molecule ,Transition Temperature ,Urea ,Amino Acid Sequence ,Particle Size ,Protein Structure, Quaternary ,Eutectic system ,biology ,Transition temperature ,Cryoelectron Microscopy ,Water ,Recombinant Proteins ,Elastin ,Chemical engineering ,biology.protein ,Microscopy, Electron, Scanning ,Solvents ,Peptides - Abstract
Deep eutectic solvents promoted the stabilization of the collapsed state of elastin-like recombinamers - and the subsequent formation of aggregates - upon the loss of the structural water molecules involved in hydrophobic hydration. Cryo-etch scanning electron microscopy allowed the observation of these aggregates in neat deep eutectic solvents. The suppression of the lower critical solution temperature transition, observed by differential scanning calorimetry and dynamic light scattering, confirmed the presence of the elastin-like recombinamers in their collapsed state. Actually, the transition from the collapsed to the expanded state was suppressed even after moderate aqueous dilution - for water contents ranging from nil to ca. 45 wt % - and it was only recovered upon further addition of water - above 50 wt %. These features revealed the preferred stabilization of the collapsed state in not only neat deep eutectic solvents but also partially hydrated deep eutectic solvents. We consider that the capability to trigger the lower critical solution temperature transition by partial hydration of deep eutectic solvent may open interesting perspectives for nano(bio)technological applications of elastin-like recombinamers. more...
- Published
- 2012
40. Osteoconductive performance of carbon nanotube scaffolds homogeneously mineralized by flow-through electrodeposition
- Author
-
M. Luisa Ferrer, María C. Gutiérrez, Stefania Nardecchia, Francisco del Monte, M. Teresa Portolés, and M. Concepción Serrano
- Subjects
Nanotube ,Scaffold ,Materials science ,Biocompatibility ,Osteoblast ,Nanotechnology ,02 engineering and technology ,Bone healing ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,Bone tissue ,01 natural sciences ,Mineralization (biology) ,0104 chemical sciences ,Electronic, Optical and Magnetic Materials ,Biomaterials ,medicine.anatomical_structure ,Chemical engineering ,Electrochemistry ,medicine ,Surface modification ,0210 nano-technology - Abstract
The treatment of bone lesions, including fractures, tumor resection and osteoporosis, is a common clinical practice where bone healing and repair are pursued. It is widely accepted that calcium phosphate-based materials improve integration of biomaterials with surrounding bone tissue and further serve as a template for proper function of bone-forming cells. Within this context, mineralization on preformed substrates appears as an interesting and successful alternative for mineral surface functionalization. However, mineralization of >true> 3D scaffolds -in which the magnitude of the third dimension is within the same scale as the other two- is by no means a trivial issue because of the difficulty to obtain a homogeneous mineral layer deposited on the entire internal surface of the scaffold. Herein, a >flow-through> electrodeposition process is applied for mineralization of 3D scaffolds composed of multiwall carbon nanotubes and chitosan. It is demonstrated that, irrespective of the experimental conditions used for electrodeposition (e.g., time, temperature and voltages), the continuous feed of salts provided by the use of a flow-through configuration is the main issue if one desires to coat the entire internal structure of 3D scaffolds with a homogeneous mineral layer. Finally, mineralized scaffolds not only showed a remarkable biocompatibility when tested with human osteoblast cells, but also enhanced osteoblast terminal differentiation (as early as 7 days in calcifying media). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim., This work was supported by grants from MINECO (Project Numbers MAT2009-10214 and MAT2011-25329) and from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement number 263289 (Green Nano Mesh). S.N. acknowledges CSIC for a JAE-Pre fellowship. M. C. S. is greatly in debt with MINECO for a Juan de la Cierva fellowship. Fernando Pinto (from the Instituto de Ciencias Agrarias-CSIC) and Sylvia Gutierrez (from the Centro Nacional de Biotecnologia-CSIC) are acknowledged for their assistance with SEM and confocal microscopy studies, respectively. more...
- Published
- 2012
41. In Situ Precipitation of Amorphous Calcium Phosphate and Ciprofloxacin Crystals during the Formation of Chitosan Hydrogels and Its Application for Drug Delivery Purposes
- Author
-
María C. Gutiérrez, M. Luisa Ferrer, M. Concepción Serrano, Francisco del Monte, Mariella Dentini, Andrea Barbetta, and Stefania Nardecchia
- Subjects
Calcium Phosphates ,In situ ,Biocompatible polymers ,Surface Properties ,Context (language use) ,Nanotechnology ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Chitosan ,chitosan hydrogels ,amorphous calcium phosphate ,drug delivery ,ciprofloxacin ,chemistry.chemical_compound ,Drug Delivery Systems ,Electrochemistry ,General Materials Science ,Amorphous calcium phosphate ,Particle Size ,Spectroscopy ,Precipitation (chemistry) ,Hydrogels ,Surfaces and Interfaces ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,0104 chemical sciences ,chemistry ,Drug delivery ,Self-healing hydrogels ,Crystallization ,Rheology ,0210 nano-technology - Abstract
The immobilization of more than one single substance within the structure of a biocompatible polymer provides multifunctional biomaterials with attractive and enhanced properties. In the context of bone tissue engineering, it could be of great interest to synthesize a biomaterial that simultaneously contains amorphous calcium phosphate (ACP), to favor calcium and phosphate precipitation and promote osteogenesis, and an antibiotic such as ciprofloxacin (CFX) that can, eventually, avoid infections resulting after surgical scaffold implantation. However, the co-immobilization of multiple substances is by no means a trivial issue because of the enhanced number of interactions that can take place. One of the main issues is controlling not only the diverse solid forms that individual substances can eventually adopt, but also the forces responsible for the self-organization of the individual components. The latter determines whether phase-separated structures or conjugated architectures are obtained and, consequently, may dramatically affect their functionality. Herein, we have observed-by SEM, TEM, and solid-state NMR-that enzymatically-assisted coprecipitation of ACP and CFX resulted in phase-separated structures. Thus, CFX crystals showed identical morphology to that obtained in the absence of ACP, but the size was smaller. Neither the size nor the morphology of ACP exhibited significant differences whether precipitated with or without CFX, but, in the former case, ACP was stabilized over a wider range of pH and temperature. Finally, by using this methodology and the ice segregation induced self-assembly process (ISISA), we have successfully co-immobilized ACP and CFX in chitosan-based scaffolds. Interestingly, the presence of ACP exerted significant control on the CFX release from these materials. more...
- Published
- 2012
42. Deep-eutectic-solvent-assisted synthesis of hierarchical carbon electrodes exhibiting capacitance retention at high current densities
- Author
-
Ricardo Jiménez, Francisco del Monte, Daniel Carriazo, María C. Gutiérrez, M. Luisa Ferrer, Fernando Picó, Aitana Tamayo, and José M. Rojo
- Subjects
Supercapacitor ,Nanotubes, Carbon ,Organic Chemistry ,Inorganic chemistry ,chemistry.chemical_element ,Ionic Liquids ,General Chemistry ,Conductivity ,Capacitance ,Carbon ,Catalysis ,Deep eutectic solvent ,Choline ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,Electrode ,Solvents ,Porosity ,Electrodes - Published
- 2011
43. Progress in bionanocomposite and bioinspired foams
- Author
-
Eduardo Ruiz-Hitzky, Francisco del Monte, Pilar Aranda, Margarita Darder, M. Luisa Ferrer, and María C. Gutiérrez
- Subjects
Biomimetic materials ,Materials science ,Mechanics of Materials ,Mechanical Engineering ,Nanomedicine ,General Materials Science ,Nanotechnology ,Bioinspiration - Abstract
Significant progress is described in the development of cellular solids, specifically functional and multifunctional foams, prepared by bioinspired approaches and consisting of green components. This article covers recent examples mainly developed at the Materials Science Institute of Madrid, ICMM-CSIC, on bionanocomposites and bioinspired materials conformed as foams. These novel hierarchical porous systems bring out a broad range of advanced applications from biomedical purposes to energy generation and storage. Recent progress in the development of advanced bionanocomposite and bioinspired foams with controlled porosity and low relative density is paving the way towards applications in a wide range of fields, from energy storage and insulating materials with reduced flammability for application in building and transport productivity sectors to novel scaffolds for tissue engineering and other biomedical purposes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim., E. R.-H., P. A., and M. D. are grateful for funding from CICYT (Spain), projects MAT2009-09960 and NAN2007-31173-E, and from CSIC-Academie Hassan II, project 2010MA0003. F.d.M., M. L. F., and M. C. G. acknowledge support from MICINN grant nos. MAT2009-10214 and PET2008-0168-01. more...
- Published
- 2011
44. Deep eutectic solvents as both precursors and structure directing agents in the synthesis of nitrogen doped hierarchical carbons highly suitable for CO2 capture
- Author
-
M. Luisa Ferrer, María C. Gutiérrez, Francisco del Monte, Daniel Carriazo, José B. Parra, Conchi O. Ania, Centre de Recherche sur la Matière Divisée (CRMD), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO), The City College of New York (CCNY), City University of New York [New York] (CUNY), Instituto Nacional del Carbon (INCAR), Instituto Nacional del Carbón, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto Nacional del Carbon, and CSIC-Oviedo more...
- Subjects
Sorbent ,Inorganic chemistry ,chemistry.chemical_element ,02 engineering and technology ,Resorcinol ,010402 general chemistry ,01 natural sciences ,chemistry.chemical_compound ,Environmental Chemistry ,ComputingMilieux_MISCELLANEOUS ,Eutectic system ,Renewable Energy, Sustainability and the Environment ,Carbonization ,[SDE.IE]Environmental Sciences/Environmental Engineering ,Chemical process of decomposition ,Sorption ,[CHIM.CATA]Chemical Sciences/Catalysis ,[CHIM.MATE]Chemical Sciences/Material chemistry ,021001 nanoscience & nanotechnology ,Pollution ,Nitrogen ,0104 chemical sciences ,Nuclear Energy and Engineering ,chemistry ,0210 nano-technology ,Choline chloride - Abstract
Deep eutectic solvents (DESs) have been used in the synthesis of nitrogen-doped carbons exhibiting a hierarchical porous structure. The CO2 sorption capacity of these solid sorbents was extraordinary because of their relatively high nitrogen content and their bimodal porous structure where micropores provide high surface areas (ca. 700 m2 g−1) and macropores provide accessibility to such a surface. DESs were composed of resorcinol, 3-hydroxypyridine and choline chloride in 2 : 2 : 1 and 1 : 1 : 1 molar ratios. Polycondensation of resorcinol and 3-hydroxypyridine (with formaldehyde) promoted DES segregation in a spinodal-like decomposition process by the formation of a polymer rich phase and a depleted polymer phase. Thus, DESs played a multiple role in the synthetic process; the liquid medium that ensured reagents homogenization, the structure-directing agent that is responsible for the achievement of the hierarchical structure, and the source of carbon and nitrogen of the solid sorbent obtained after carbonization. Interestingly, the homogeneous incorporation of nitrogen at the solution stage of the synthetic process (rather than by post-treatment of the preformed carbon) allowed the achievement of significant nitrogen contents even in carbons obtained at relatively high temperatures (e.g. 8–12 at% for 600 °C and ca. 5 at% for 800 °C). It is worth noting that, despite thermal treatments at high temperatures tend to decrease the nitrogen content, the high surface area of the solid sorbents obtained at 800 °C contributed to a significant enhancement of CO2 capture while providing superior selectivity, recyclability and stability. more...
- Published
- 2011
- Full Text
- View/download PDF
45. Enzyme-induced graft polymerization for preparation of hydrogels: synergetic effect of laccase-immobilized-cryogels for pollutants adsorption
- Author
-
María C. Gutiérrez, M. Luisa Ferrer, Carmen Peinado, Marina Nieto, Fernando Catalina, Francisco del Monte, C. Abrusci, Stefania Nardecchia, Ministerio de Economía y Competitividad (España), and Consejo Superior de Investigaciones Científicas (España) more...
- Subjects
Laccase ,biology ,Immobilized enzyme ,Chemistry ,technology, industry, and agriculture ,Substrate (chemistry) ,General Chemistry ,macromolecular substances ,Condensed Matter Physics ,Adsorption ,Polymerization ,Chemical engineering ,Self-healing hydrogels ,biology.protein ,Copolymer ,Organic chemistry ,Glucose oxidase - Abstract
The use of polyethylene oxide-polypropylene oxide-polyethylene oxide block-copolymers as a mediator in the laccase-induced graft polymerization of diacrylic derivate of polyethylene glycols resulted in the formation of PEG-g-F68 hydrogels. The proper oxygen content in the reaction medium to obtain reasonable polymerization conversions (i.e., on one hand, laccase needs oxygen as substrate whereas, on the other, oxygen is a strong inhibitor of radical polymerizations) was achieved by the use of an enzymatic scavenging system consisting of glucose oxidase and glucose. Eventually, laccase was immobilized within the resulting PEG-g-F68 hydrogel with full preservation of enzyme activity. Laccases have been used for bioremediation purposes because of their ability to degrade phenolic compounds. Thus, laccase-immobilized PEG-g-F68 hydrogels were submitted to the ISISA (ice segregation induced self-assembly) process for preparation of laccase-immobilized PEG-g-F68 cryogels which exhibited a macroporous structure where immobilized laccase preserved almost total activity (ca. 90%) for a period exceeding three months after preparation. Synergy between macroporous structure (deriving from the ISISA process), amphiphilic domains (deriving from graft copolymer) and activity of the immobilized enzyme provided outstanding adsorption capabilities to the cryogels (up to 235 mg g(-1)), This work was supported by MICINN (MAT2009-10214, MAT2009-09671 and PET2008-0168-01) and CSIC (200660F011). M. N. and S. N. thank CSIC for a research contract and a PhD fellowship, respectively. C. A. thanks MICINN for a Ramon y Cajal contract. We thank F. Pinto for assistance with SEM. more...
- Published
- 2010
46. The conformation of serum albumin in solution: a combined phosphorescence depolarization-hydrodynamic modeling study
- Author
-
José García de la Torre, Ricardo Duchowicz, A. Ulises Acuña, B. Carrasco, and M. Luisa Ferrer
- Subjects
Glycerol ,Models, Molecular ,Time Factors ,Protein Conformation ,Serum albumin ,Biophysics ,Thermodynamics ,Biophysical Phenomena ,Crystal ,Protein structure ,medicine ,Animals ,Humans ,Rotational correlation time ,Serum Albumin ,Crystallography ,biology ,Chemistry ,Rotational diffusion ,Water ,Depolarization ,Serum Albumin, Bovine ,Hydrogen-Ion Concentration ,Models, Theoretical ,Human serum albumin ,Erythrosine ,Spectrophotometry ,biology.protein ,Cattle ,Phosphorescence ,medicine.drug ,Protein Binding ,Research Article - Abstract
There is a striking disparity between the heart-shaped structure of human serum albumin (HSA) observed in single crystals and the elongated ellipsoid model used for decades to interpret the protein solution hydrodynamics at neutral pH. These two contrasting views could be reconciled if the protein were flexible enough to change its conformation in solution from that found in the crystal. To investigate this possibility we recorded the rotational motions in real time of an erythrosin-bovine serum albumin complex (Er-BSA) over an extended time range, using phosphorescence depolarization techniques. These measurements are consistent with the absence of independent motions of large protein segments in solution, in the time range from nanoseconds to fractions of milliseconds, and give a single rotational correlation time phi(BSA, 1 cP, 20 degrees C) = 40 +/- 2 ns. In addition, we report a detailed analysis of the protein hydrodynamics based on two bead-modeling methods. In the first, BSA was modeled as a triangular prismatic shell with optimized dimensions of 84 x 84 x 84 x 31.5 A, whereas in the second, the atomic-level structure of HSA obtained from crystallographic data was used to build a much more refined rough-shell model. In both cases, the predicted and experimental rotational diffusion rate and other hydrodynamic parameters were in good agreement. Therefore, the overall conformation in neutral solution of BSA, as of HSA, should be rigid, in the sense indicated above, and very similar to the heart-shaped structure observed in HSA crystals. more...
- Published
- 2001
47. Three-dimensional microchanelled electrodes in flow-through configuration for bioanode formation and current generation
- Author
-
Dónal Leech, Ricardo Jiménez, María C. Gutiérrez, Francisco del Monte, Krishna P. Katuri, and M. Luisa Ferrer
- Subjects
Materials science ,Microbial fuel cell ,Nanocomposite ,Renewable Energy, Sustainability and the Environment ,Nanotechnology ,Carbon nanotube ,Pollution ,law.invention ,Nuclear Energy and Engineering ,Chemical engineering ,law ,Electrode ,Environmental Chemistry ,Current (fluid) ,Electrical conductor ,Current density ,Power density - Abstract
Three-dimensional microchannelled nanocomposite electrodes fabricated by ice-segregation induced self-assembly of chitosan-dispersed multiwall carbon nanotubes are shown to provide a scaffold for growth of electroactive bacteria for use as acetate-oxidizing bioanodes in bioelectrochemical systems. The hierarchical structure provides a conductive surface area available for G. sulfurreducens colonization, with a flow through configuration along the electrode providing a substrate for bacterial colonization and bio-electrochemical processes. This configuration, whilst resulting in sub-monolayer biofilm coverage over the three-dimensional surface, is capable of providing acetate oxidation current densities of up to 24.5 A m−2, equating to a volumetric current density of 19 kA m−3, in the flow-through configuration. Such bioanodes, when operated in non-optimized flow-through microbial fuel cell configuration, provide a maximum power density of 2.87 W m−2, which is equivalent to 2.0 kW m−3 volumetric power density. more...
- Published
- 2011
- Full Text
- View/download PDF
48. Chitosan Gelation Induced by the in Situ Formation of Gold Nanoparticles and Its Processing into Macroporous Scaffolds.
- Author
-
María J. Hortigüela, Inmaculada Aranaz, María C. Gutiérrez, M. Luisa Ferrer, and Francisco del Monte
- Published
- 2011
- Full Text
- View/download PDF
Discovery Service for Jio Institute Digital Library
For full access to our library's resources, please sign in.