30 results on '"Davide Blasi"'
Search Results
2. Revealing the effects of the ball milling pretreatment on the ethanosolv fractionation of lignin from walnut and pistachio shells
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Davide Blasi, Davide Mesto, Pietro Cotugno, Cosima D. Calvano, Marco Lo Presti, and Gianluca M. Farinola
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Ball milling ,lignin first ,endocarp shells ,organosolv lignin ,hardwood lignin ,Science ,Chemistry ,QD1-999 - Abstract
In this work, a detailed study on the ethanosolv lignin fractionation from endocarps, aiming at understanding the role played by the ball milling (BM) pretreatment, is presented. Walnut and pistachio shells were chosen as a case study, since they exhibit excellent mechanical properties and their tissues have been extensively studied in terms of structure, composition, and lignin distribution. Here, it was demonstrated that the BM pretreatment is not particularly suited for these biomasses, since it is not able to promote the lignin fractionation from the whole tissue, and additionally, it triggers the oxidation of the substrate. Although in the case of walnut shell this oxidation can be prevented thanks to the remarkable radical scavenger activity (RSA) of its extractives, in the case of pistachio shell the BM is responsible for a partial lignin condensation. Pistachio shells resulted a particularly attractive feedstock since they can be easily delignified using mild ethanosolv processes, leading to highly regular lignin fractions, rich in S units (86%) and β-O-4 linking motif (>60% C9 units), so particularly suited for the chemical upgrading to added-value aromatics.
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- 2022
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3. Controlling the Binding Efficiency of Surface Confined Antibodies through the Design of Mixed Self‐Assembled Monolayers
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Lucia Sarcina, Pietro Delre, Giovanni Graziano, Angela Stefanachi, Davide Blasi, Rosaria A. Picca, Cinzia Di Franco, Francesco Leonetti, Gaetano Scamarcio, Paolo Bollella, Giuseppe F. Mangiatordi, Eleonora Macchia, and Luisa Torsi
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density functional theory ,HIV1 p24 detection ,mixed self‐assembled monolayers ,surface plasmon resonance ,Physics ,QC1-999 ,Technology - Abstract
Abstract A plethora of different electronic and optoelectronic devices have been developed lately, for biosensing applications (e.g., label‐free, fast, and easier to operate) based on a detecting interface accommodating the biorecognition elements, anchored by thiolate self‐assembled monolayers (SAMs) on a gold surface. Here, a surface plasmon resonance (SPR) characterization of anti‐p24 anchored on different SAMs is performed to investigate the effect of the SAM structure on the antibodies’ packing efficiency and the sensors’ analytical figures of merit. Notably, the mixed SAM deposited from a solution 10:1 of 3‐mercaptopropionic acid and 11‐mercaptoundecanoic acid (11MUA) is compared to that resulting from a solution 10:1 of ad hoc synthesized N‐(2‐hydroxyethyl)‐3‐mercaptopropanamide (NMPA)/11MUA. Despite the improvement in the anti‐p24 surface coverage registered using the 11MUA/NMPA SAM, the latter produces a significant decrease in the antibodies’ binding efficiency against human immunodeficiency virus p24 protein. To provide a molecular rationale behind the SPR data, density functional theory calculations are also undertaken. A comprehensive physical view of the main competing phenomena affecting the biorecognition events at a biofunctionalized gold detecting interface is represented here.
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- 2023
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4. The Effect of Milling on the Ethanolic Extract Composition of Dried Walnut (Juglans regia L.) Shells
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Giovanni Ventura, Davide Mesto, Davide Blasi, Tommaso R. I. Cataldi, and Cosima Damiana Calvano
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biomass ,epoxidation ,fatty acids ,LC-MS/MS ,mill grinding ,phenols ,Biology (General) ,QH301-705.5 ,Chemistry ,QD1-999 - Abstract
This study investigates the ethanolic extract of dried walnut (Juglans regia L.) shells upon hammer milling (HM) and ball milling (BM) grinding processes. Marked differences were observed in the attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectra. The two extracts were investigated by reversed-phase liquid chromatography coupled with electrospray ionization and high-resolution mass spectrometry (RPLC-ESI-HRMS). Following enzymatic digestion, the fatty acids (FAs) were examined, and tandem MS of epoxidized species was applied to establish the C-C double bond position; the most abundant species were FA 18:2 Δ9,12, FA 18:1 Δ9, and FA 18:3 Δ9,12,15. However, no significant qualitative differences were observed between FAs in the two samples. Thus, the presence of potential active secondary metabolites was explored, and more than 30 phenolic compounds, including phenols, ellagic acid derivatives, and flavonoids, were found. Interestingly, the HM samples showed a high concentration of ellagitannins and hydrolyzable tannins, which were absent in the BM sample. These findings corroborate the greater phenolic content in the HM sample, as evaluated by the Folin–Ciocalteu test. Among the others, the occurrence of lanceoloside A at m/z 391.1037 [C19H20O9-H]−, and a closely related benzoyl derivate at m/z 405.1190 (C20H22O9-H]−), was ascertained. The study provides valuable information that highlights the significance of physical pre-treatments, such as mill grinding, in shaping the composition of extracts, with potential applications in the biorefinery or pharmaceutical industries.
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- 2023
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5. Enhancing the Sensitivity of Biotinylated Surfaces by Tailoring the Design of the Mixed Self-Assembled Monolayer Synthesis
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Davide Blasi, Lucia Sarcina, Angelo Tricase, Angela Stefanachi, Francesco Leonetti, Domenico Alberga, Giuseppe Felice Mangiatordi, Kyriaki Manoli, Gaetano Scamarcio, Rosaria Anna Picca, and Luisa Torsi
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Chemistry ,QD1-999 - Published
- 2020
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6. Electrochemical and X-ray Photoelectron Spectroscopy Surface Characterization of Interchain-Driven Self-Assembled Monolayer (SAM) Reorganization
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Angelo Tricase, Anna Imbriano, Nicoletta Ditaranto, Eleonora Macchia, Rosaria Anna Picca, Davide Blasi, Luisa Torsi, and Paolo Bollella
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self-assembled monolayers ,cyclic voltammetry ,X-ray photoelectron spectroscopy ,conformational rearrangements ,single-molecule detection ,Chemistry ,QD1-999 - Abstract
Herein, we report a combined strategy encompassing electrochemical and X-ray photoelectron spectroscopy (XPS) experiments to investigate self-assembled monolayer (SAM) conformational reorganization onto an electrode surface due to the application of an electrical field. In particular, 3-mercaptopriopionic acid SAM (3MPA SAM) modified gold electrodes are activated with a 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysulfosuccinimide (NHSS) (EDC-NHSS) mixture by shortening the activation time, from 2 h to 15/20 min, labelled as Protocol-A, -B and -C, respectively. This step, later followed by a deactivation process with ethanolamine (EA), plays a key role in the reaction yields (formation of N-(2-hydroxyethyl)-3-mercaptopropanamide, NMPA) but also in the conformational rearrangement observed during the application of the electrical field. This study aims at explaining the high performance (i.e., single-molecule detection at a large electrode interface) of bioelectronic devices, where the 3MPA-based SAM structure is pivotal in achieving extremely high sensing performance levels due to its interchain interaction. Cyclic voltammetry (CV) experiments performed in K4Fe(CN)6:K3Fe(CN)6 for 3MPA SAMs that are activated/deactivated show similar trends of anodic peak current (IA) over time, mainly related to the presence of interchain hydrogen bonds, driving the conformational rearrangements (tightening of SAMs structure) while applying an electrical field. In addition, XPS analysis allows correlation of the deactivation yield with electrochemical data (conformational rearrangements), identifying the best protocol in terms of high reaction yield, mainly related to the shorter reaction time, and not triggering any side reactions. Finally, Protocol-C’s SAM surface coverage, determined by CV in H2SO4 and differential pulse voltammetry (DPV) in NaOH, was 1.29 * 1013 molecules cm−2, being similar to the bioreceptor surface coverage in single-molecule detection at a large electrode interface.
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- 2022
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7. A label-free immunosensor based on a graphene water-gated field-effect transistor.
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Rosaria Anna Picca, Davide Blasi, Eleonora Macchia, Kyriaki Manoli, Cinzia Di Franco, Gaetano Scamarcio, Fabrizio Torricelli, Amaia Zurutuza, Ilargi Napal, Alba Centeno, and Luisa Torsi
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- 2019
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8. Ratiometric Nanothermometer Based on a Radical Excimer for In Vivo Sensing
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Davide Blasi, Nerea Gonzalez‐Pato, Xavier Rodriguez Rodriguez, Iñigo Diez‐Zabala, Sumithra Yasaswini Srinivasan, Núria Camarero, Oriol Esquivias, Mònica Roldán, Judith Guasch, Anna Laromaine, Pau Gorostiza, Jaume Veciana, and Imma Ratera
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Biomaterials ,Nanomedicine ,Cèl·lules ,Cells ,Nanomedicina ,General Materials Science ,General Chemistry ,Biotechnology - Abstract
Ratiometric fluorescent nanothermometers with near-infrared emission play an important role in in vivo sensing since they can be used as intracellular thermal sensing probes with high spatial resolution and high sensitivity, to investigate cellular functions of interest in diagnosis and therapy, where current approaches are not effective. Herein, the temperature-dependent fluorescence of organic nanoparticles is designed, synthesized, and studied based on the dual emission, generated by monomer and excimer species, of the tris(2,4,6-trichlorophenyl)methyl radical (TTM) doping organic nanoparticles (TTMd-ONPs), made of optically neutral tris(2,4,6-trichlorophenyl)methane (TTM-αH), acting as a matrix. The excimer emission intensity of TTMd-ONPs decreases with increasing temperatures whereas the monomer emission is almost independent and can be used as an internal reference. TTMd-ONPs show a great temperature sensitivity (3.4% K-1 at 328 K) and a wide temperature response at ambient conditions with excellent reversibility and high colloidal stability. In addition, TTMd-ONPs are not cytotoxic and their ratiometric outputs are unaffected by changes in the environment. Individual TTMd-ONPs are able to sense temperature changes at the nano-microscale. In vivo thermometry experiments in Caenorhabditis elegans (C. elegans) worms show that TTMd-ONPs can locally monitor internal body temperature changes with spatio-temporal resolution and high sensitivity, offering multiple applications in the biological nanothermometry field.© 2023 The Authors. Small published by Wiley-VCH GmbH.
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- 2023
9. Tuning the Electro‐Optical Properties of Mixed‐Halide Trityl Radicals Bearing para ‐Brominated Positions through Halogen Substitution
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Davide Mesto, Yasi Dai, Carlo N. Dibenedetto, Angela Punzi, Jozef Krajčovič, Marinella Striccoli, Fabrizia Negri, Davide Blasi, Mesto, D, Dai, Y, Dibenedetto, CN, Punzi, A, Krajcovic, J, Striccoli, M, Negri, F, and Blasi, D
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Organic Chemistry ,Trityl radicals ,Physical and Theoretical Chemistry ,Open-shell specie ,Doublet emitter ,Fluorinated compound - Abstract
In this work, the synthesis and characterization of two new trityl radicals bearing two p-brominated positions, i. e. the 2,2 '-((perchlorophenyl)methylene)bis(1,3,5-tribromobenzene) radical and the 6,6 '-((perchlorophenyl)methylene)bis(3-bromo-1,2,4,5-tetrafluorobenzene) radical, are presented. Slightly modifying the strategy typically used for the synthesis of non-symmetric mixed-halide trityl radicals, we were able to considerably increase the reaction yield for the radical precursors. In addition, for the first time the electro-optical properties of a highly fluorinated trityl radical were studied, achieving the most blue-shifted emission for a trityl radical reported up to now. Quantum-chemical calculations carried out to supplement the experimental investigation support the electrochemical and spectroscopic data as well as rationalize the observed blue shift of the highly fluorinated species.
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- 2022
10. Negatively charged ions to probe self-assembled monolayer reorganization driven by interchain interactions
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Angela Stefanachi, Luisa Torsi, Gaetano Scamarcio, Eleonora Macchia, Paolo Bollella, Francesco Leonetti, Alessandro Favia, Davide Blasi, Rosaria Anna Picca, and Angelo Tricase
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Materials science ,Hydrogen bond ,Self-assembled monolayer ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Hydrophobic effect ,Dipole ,Chemical physics ,Electric field ,Phase (matter) ,Monolayer ,Materials Chemistry ,Cyclic voltammetry ,0210 nano-technology - Abstract
A combined cyclic voltammetry (CV) and grazing angle attenuated total reflectance (GA-ATR) IR study on the interchain interaction driven reorganization of self-assembled monolayers (SAMs) in an electric field was presented. The study focused on an N-(2-hydroxyethyl)-3-mercaptopropanamide (NMPA) SAM endowed with interchain hydrogen bonding, strongly affected by an external electric field interacting with the dipole moment associated with the hydrogen bonding. Conversely, a 1-hexanethiol SAM was characterized by interchain hydrophobic interaction not affected by the applied field. These features were demonstrated by means of reiterated CV experiments involving an electroactive negatively charged probe, namely Fe(CN)64−, and a Au-SAM serving as a working electrode. The diffusional/interpenetration and kinetics parameters provided the apparent electron transfer rate constant (k0) values. For the NMPA, the interchain rearrangement kinetics was that of an ion-permeable layer that reached, in the electric field, a steady-state configuration after about 50 minutes. The 1-hexanethiol chains’ reorganization exhibited more complex kinetics involving a first phase (ca. 50 minutes) of an ion-permeable phase followed by a sharp decrease in the anodic peak current related to the tightening of the structure, likely due to the interchain hydrophobic interaction, hindering ion diffusion. The change in the SAM structure upon cycling in the electric field was confirmed by the GA-ATR measurements.
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- 2021
11. Enhancing the Sensitivity of Biotinylated Surfaces by Tailoring the Design of the Mixed Self-Assembled Monolayer Synthesis
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Gaetano Scamarcio, Domenico Alberga, Lucia Sarcina, Davide Blasi, Luisa Torsi, Rosaria Anna Picca, Francesco Leonetti, Angelo Tricase, Kyriaki Manoli, Giuseppe Felice Mangiatordi, and Angela Stefanachi
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Streptavidin ,chemistry.chemical_classification ,Analyte ,General Chemical Engineering ,Biomolecule ,Self-assembled monolayer ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Combinatorial chemistry ,Article ,0104 chemical sciences ,chemistry.chemical_compound ,Chemistry ,chemistry ,Biotinylation ,Surface modification ,MD Simulations ,Surface plasmon resonance ,0210 nano-technology ,Biosensor ,QD1-999 - Abstract
Thiolated self-assembled monolayers (SAMs) are typically used to anchor on a gold surface biomolecules serving as recognition elements for biosensor applications. Here, the design and synthesis of N-(2-hydroxyethyl)-3-mercaptopropanamide (NMPA) in biotinylated mixed SAMs is proposed as an alternative strategy with respect to on-site multistep functionalization of SAMs prepared from solutions of commercially available thiols. In this study, the mixed SAM deposited from a 10:1 solution of 3-mercaptopropionic acid (3MPA) and 11-mercaptoundecanoic acid (11MUA) is compared to that resulting from a 10:1 solution of NMPA:11MUA. To this end, surface plasmon resonance (SPR) and attenuated total reflectance infrared (ATR-IR) experiments have been carried out on both mixed SAMs after biotinylation. The study demonstrated how the fine tuning of the SAM features impacts directly on both the biofunctionalization steps, i.e., the biotin anchoring, and the biorecognition properties evaluated upon exposure to streptavidin analyte. Higher affinity for the target analyte with reduced nonspecific binding and lower detection limit has been demonstrated when NMPA is chosen as the more abundant starting thiol. Molecular dynamics simulations complemented the experimental findings providing a molecular rationale behind the performance of the biotinylated mixed SAMs. The present study confirms the importance of the functionalization design for the development of a highly performing biosensor.
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- 2020
12. New insights in luminescent fluorinated transition metal compounds
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Giorgio Rizzo, Davide Blasi, Roberta Ragni, and Gianluca M. Farinola
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- 2022
13. Novel adamantane substituted polythiophenes as competitors to Poly(3-Hexylthiophene)
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Jan Jančík, Jan Pospíšil, Matouš Kratochvíl, Jan Truksa, Davide Altamura, Cinzia Giannini, Martin Weiter, Davide Blasi, Vladimír Lukeš, Eric D. Głowacki, and Jozef Krajčovič
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Polymers and Plastics ,Organic Chemistry ,Materials Chemistry - Published
- 2022
14. Fast E/Z UV-light response T-type photoswitching of phenylene-thienyl imines
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Dominik Veselý, Ján Jančík, Martin Weiter, Davide Blasi, Nikoleta Ivanova, Jozef Krajčovič, and Anton Georgiev
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General Chemical Engineering ,General Physics and Astronomy ,General Chemistry - Published
- 2022
15. Peripherical thioester functionalization induces
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Angela, Punzi, Davide, Blasi, Alessandra, Operamolla, Roberto, Comparelli, Gerardo, Palazzo, and Gianluca M, Farinola
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In this work we demonstrated that the peripherical thioacetylation of a bithiophene-DPP molecule can greatly influence the solid-state properties triggering the formation of NIR emitting
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- 2021
16. Ultimately Sensitive Organic Bioelectronic Transistor Sensors by Materials and Device Structures' Design
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Fabrizio Torricelli, Eleonora Macchia, Lucia Sarcina, Davide Blasi, Kyriaki Manoli, Nicola Cioffi, Cinzia Di Franco, Ronald Österbacka, Luisa Torsi, Gaetano Scamarcio, and Rosaria Anna Picca
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organic bioelectronics ,Materials science ,Transistor ,biomarkers ,Nanotechnology ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,biosensors ,sensors ,01 natural sciences ,0104 chemical sciences ,Electronic, Optical and Magnetic Materials ,law.invention ,Biomaterials ,law ,Electrochemistry ,organic field-effect transistors ,0210 nano-technology - Published
- 2020
17. About the amplification factors in organic bioelectronic sensors
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Nicola Cioffi, Cinzia Di Franco, Kyriaki Manoli, Rosaria Anna Picca, Eleonora Macchia, Ronald Österbacka, Gaetano Scamarcio, Luisa Torsi, Nicoletta Ditaranto, Lucia Sarcina, Fabrizio Torricelli, and Davide Blasi
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Analyte ,Materials science ,Process Chemistry and Technology ,Transistor ,Nanotechnology ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Organic bioelectronic electrolyte-gated large transistorsOrganic bioelectronicsSingle-molecule bioanalytical technologies ,0104 chemical sciences ,Electrochemical gas sensor ,law.invention ,Mechanics of Materials ,law ,General Materials Science ,Electrical and Electronic Engineering ,0210 nano-technology ,Biosensor - Abstract
Several three-terminal organic bioelectronic structures have been proposed so far to address the needs for a variety of biosensing applications. The most popular ones utilized organic field-effect transistors operated in an electrolyte, to detect both proteins and genomic analytes. They are endowed with selectivity by immobilizing a layer of bio-recognition elements. These features along with the foreseen low-cost for their production, make them very appealing for point-of-care biomedical applications. However, organic bioelectronic transistors do not always exhibit a performance level beyond state-of-the-art electrochemical sensors, which have been dominating the field for decades. This review offers a perspective view based on a systematic comparison between the potentiometric and amperometric electrochemical sensors and their organic bioelectronic transistor counterparts. The key-relevant aspects of the sensing mechanisms are reviewed for both, and when the mathematical analytical expression is actually available, the amplification factors are reported as the ratio between the response of a rationally designed transistor (or amplifying circuit) and that of a homologous electrochemical sensor. The functional dependence of the bioelectronic sensor responses on the concentration of the species to be detected enabling their correct analytical quantification, is also addressed.
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- 2020
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18. Printed, cost-effective and stable poly(3-hexylthiophene) electrolyte-gated field-effect transistors
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Zahra Gounani, Zsolt Miklos Kovacs Vajna, Rosaria Anna Picca, Francesco Modena, Mario Caironi, Amit Tewari, Ronald Österbacka, Fabrizio Antonio Viola, Axel Luukkonen, Gaetano Scamarcio, Davide Blasi, Fabrizio Torricelli, Luisa Torsi, and Eleonora Macchia
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Materials science ,business.industry ,Transistor ,Stacking ,02 engineering and technology ,General Chemistry ,Electrolyte ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Evaporation (deposition) ,0104 chemical sciences ,Amorphous solid ,law.invention ,Organic semiconductor ,law ,Electrode ,Materials Chemistry ,Optoelectronics ,Field-effect transistor ,0210 nano-technology ,business - Abstract
Organic bioelectronic sensors based on an electrolyte gated field-effect transistor are gaining momentum due to their extraordinary high-performance level that enables label-free selective single-molecule detection of both genomic and protein biomarkers with a millimeter-wide electrolyte-gated field-effect transistor (EGOFET) device. The organic semiconductor channel material used so far is a spin-coated regio-regular poly(3-hexylthiophene) (P3HT). Of paramount importance is to design an EGOFET sensor that is stable and cost-effective. To address the latter feature, an ink-jet printed regio-regular P3HT film is here investigated as the channel material. Moreover, the EGOFET device structure is intended to comprise a coplanar lateral gate electrode that enables mechanical and electrical stability. Overall, the structure is compatible with large area processing so it can be fabricated at low-costs and can be operated continuously for eight days. Additionally, systematic optical and Raman characterization of the P3HT film proves that the printing process results in a film with a low energetic disorder (better π–π stacking in the crystalline regions) that likely enables stable operation. However, the higher quality crystalline regions (as compared to a spin-coated film) are dispersed in a more significant fraction of the amorphous disordered material with a larger amount of trap states. The higher crystalline order is ascribed to the higher boiling point and slower evaporation of the ortho-dichlorobenzene solvent used in the printing process. Overall, the present study provides a systematic insight into the structure–property correlations, essential to design a well-functioning and cost-effective EGOFET for high-performance electronic biosensing. It also provides one of the few investigations comparing the features characterizing a spin-coated and an ink-jet printed P3HT film.
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- 2020
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19. An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
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Jaume Veciana, Vicente G. Jiménez, Teodor Parella, Davide Blasi, Imma Ratera, Araceli G. Campaña, Paula Mayorga-Burrezo, Dirección General de Investigación Científica y Técnica, DGICT (España), Generalitat de Catalunya, Ministerio de Economía y Competitividad (España), European Research Council, Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España), and Instituto de Salud Carlos III
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010405 organic chemistry ,Chemistry ,European research ,Organic Chemistry ,European Regional Development Fund ,Library science ,circularly polarized luminescence ,General Chemistry ,Radicals ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,3. Good health ,Racemization barrier ,Bromine substituents ,Trityl radical ,media_common.cataloged_instance ,Christian ministry ,European union ,Crcularly polarized luminescence ,Research center ,media_common - Abstract
A new persistent organic free radical has been synthetized with Br atoms occupying the ortho‐ and para‐positions of a trityl core. After the isolation of its two propeller‐like atropisomers, Plus (P) and minus (M), their absolute configurations were assigned by a combination of theoretical and experimental data. Remarkably, no hints of racemization were observed up to 60 °C for more than two hours, due to the higher steric hindrance imposed by the bulky Br atoms. Therefore, when compared to its chlorinated homologue (t1/2=18 s at 60 °C), an outstanding stability against racemization was achieved. A circularly polarized luminescence (CPL) response of both enantiomers was detected. This free radical shows a satisfactory luminescent dissymmetry factor (|glum(592 nm)|≈0.7×10−3) despite its pure organic nature and low luminescence quantum yield (LQY). Improved organic magnetic CPL emitters derived from the reported structure can be envisaged thanks to the wide possibilities that Br atoms at para‐positions offer for further functionalization., The authors are grateful for the financial support received from: MOTHER (MAT2016‐80826‐R) and FANCY (CTQ2016‐80030‐R) projects, granted by the DGI (Spain), GenCat (2017‐SGR‐918) financed by DGR (Catalunya) and the Spanish Ministry of Economy and Competitiveness (PGC2018‐095808‐B‐I00 and PGC2018‐101181‐B‐I00 projects) and through the „Severo Ochoa“ Programme for Centres of Excellence in R&D (SEV‐2015‐0496) and through the „Proyecto Interdisciplinar de Frontera“, FIP‐2018 HECTIC‐PTM. We acknowledge the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (ERC‐2015‐STG‐677023). This study has been also supported by the Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER‐BBN), an initiative funded by the VI National R&D&I Plan 2008–2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. P.M.B. gratefully acknowledges financial support from the Juan de la Cierva‐Formación 2015 programme (FJCI‐2015–23577) supported by MINECO and, together with J.V, A.G.C. is grateful for a RyC‐2013–12943 contract from MINECO. We also thank the Servei de Ressonància Magnètica Nuclear, Universitat Autònoma de Barcelona, for allocating instrument time to this project.
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- 2020
20. Organic Free Radicals as Circularly Polarized Luminescence Emitters
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Vicente G. Jiménez, Davide Blasi, Araceli G. Campaña, Imma Ratera, Jaume Veciana, and Paula Mayorga Burrezo
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Atropisomer ,Circular dichroism ,Materials science ,010405 organic chemistry ,Radical ,Absolute configuration ,General Chemistry ,General Medicine ,010402 general chemistry ,Molecular physics ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Luminescence ,Absorption (electromagnetic radiation) ,Conformational isomerism ,Open shell - Abstract
Chiroptical properties of two chiral atropisomers of propeller‐like trityl‐based radical derivatives have been analyzed. A new absolute configuration (AC) assignment has been made, according to the combination of experimental and theoretical data. In this sense, their ACs have been determined through the comparison of the Cotton effects recorded by electronic circular dichroism (ECD) with the theoretical ECD of the open shell structures obtained by TD‐DFT calculations. Finally, their circularly polarized luminescence (CPL) responses have been addressed. Remarkably, this is the first description of organic free radicals as intrinsic CPL emitters. Opposite signed CPL has been detected for each pair of conformers, with acceptable luminescent dissymmetry factors (|glum|≈0.5–0.8×10−3) considering their pure organic nature. In fact, highly efficient chiral emissions have been demonstrated, according to the comparison of |glum| with their respective absorption anisotropy factors (|gabs|). This pioneering study lays the foundations for the optimization of new magnetically active organic chiral emitters.
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- 2019
21. A label-free immunosensor based on a graphene water-gated field-effect transistor
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Cinzia Di Franco, Amaia Zurutuza, Luisa Torsi, Alba Centeno, Rosaria Anna Picca, Kyriaki Manoli, Gaetano Scamarcio, Davide Blasi, Fabrizio Torricelli, Eleonora Macchia, and Ilargi Napal
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biosensor ,electrolyte-gated thin film transistor ,gate functionalization ,graphene ,label-free ,Materials science ,Graphene ,Transistor ,Nanotechnology ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,law.invention ,law ,Electrode ,Field-effect transistor ,0210 nano-technology ,Layer (electronics) ,Biosensor ,Label free - Abstract
Electrolyte-gated graphene field-effect transistors are here proposed for biosensing applications. To this end, a label-free immunosensor based on this technology is employed for the sensitive and selective detection of IgG. Differently from the typical approach based on the bioreceptor immobilization onto a graphene layer, in this work sensitivity in the lower femtomolar range can be reached thanks to the formation of a closely packed layer of anti-IgG receptors anchored to the gold gate electrode.
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- 2019
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22. Cover Feature: An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter (Chem. Eur. J. 17/2020)
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Jaume Veciana, Teodor Parella, Araceli G. Campaña, Paula Mayorga-Burrezo, Vicente G. Jiménez, Imma Ratera, and Davide Blasi
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Enantiopure drug ,Chemistry ,Radical ,Organic Chemistry ,Propeller ,General Chemistry ,Luminescence ,Photochemistry ,Racemization ,Catalysis ,Common emitter - Published
- 2020
23. Correction: Printed, cost-effective and stable poly(3-hexylthiophene) electrolyte-gated field-effect transistors
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Fabrizio Torricelli, Amit Tewari, Zahra Gounani, Davide Blasi, Fabrizio Antonio Viola, Mario Caironi, Ronald Österbacka, Axel Luukkonen, Francesco Modena, Zsolt Miklos Kovacs Vajna, Eleonora Macchia, Gaetano Scamarcio, Rosaria Anna Picca, and Luisa Torsi
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Materials science ,law ,business.industry ,Transistor ,Materials Chemistry ,Optoelectronics ,Field-effect transistor ,General Chemistry ,Electrolyte ,business ,law.invention - Abstract
Correction for ‘Printed, cost-effective and stable poly(3-hexylthiophene) electrolyte-gated field-effect transistors’ by Davide Blasi et al., J. Mater. Chem. C, 2020, DOI: 10.1039/d0tc03342a.
- Published
- 2020
24. Highly Stable and Red‐Emitting Nanovesicles Incorporating Lipophilic Diketopyrrolopyrroles for Cell Imaging
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Eric Vauthey, Nora Ventosa, Jaume Veciana, Emiliano Altamura, Davide Blasi, Imma Ratera, Santi Sala, Danilo Vona, Arnulf Rosspeintner, Angela Punzi, Gianluca M. Farinola, Antonio Ardizzone, Natascia Grimaldi, Dirección General de Investigación Científica y Técnica, DGICT (España), Generalitat de Catalunya, Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España), European Commission, Ministero dell'Istruzione, dell'Università e della Ricerca, Fonds National Suisse de la Recherche Scientifique, and Université de Genève
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Light ,Cell Survival ,Surface Properties ,Nanoparticle ,Nanotechnology ,Imaging agents ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Catalysis ,Fluorescence ,Nanomaterials ,Colloid ,Aggregation ,Two-photon excitation microscopy ,Cell Line, Tumor ,Humans ,Molecule ,Pyrroles ,Vesicles ,Particle Size ,Cell Proliferation ,Fluorescent Dyes ,Photons ,Chemistry ,Vesicle ,Optical Imaging ,Organic Chemistry ,Water ,General Chemistry ,Ketones ,021001 nanoscience & nanotechnology ,Nanostructures ,3. Good health ,0104 chemical sciences ,Membrane ,Solubility ,ddc:540 ,Nanoparticles ,0210 nano-technology - Abstract
Diketopyrrolopyrroles (DPPs) have recently attracted much interest as very bright and photostable red‐emitting molecules. However, their tendency to form nonfluorescent aggregates in water through the aggregation‐caused quenching (ACQ) effect is a major issue that limits their application under the microscope. Herein, two DPP molecules have been incorporated into the membrane of highly stable and water‐soluble quatsomes (QS; nanovesicles composed of surfactants and sterols), which allow their nanostructuration in water and, at the same time, limits the ACQ effect. The obtained fluorescent organic nanoparticles showed superior structural homogeneity, along with long‐term colloidal and optical stability. A thorough one‐ (1P) and two‐photon (2P) fluorescence characterization revealed the promising photophysical features of these fluorescent nanovesicles, which showed a high 1P and 2P brightness. Finally, the fluorescent QSs were used for the in vitro bioimaging of Saos‐2 osteosarcoma cell lines; this demonstrates their potential as nanomaterials for bioimaging applications., This work was financially supported by the DGI, Spain (Grant MOTHER; MAT2016‐80826‐R); AGAUR, Generalitat de Catalunya (Grant 2017 SGR 918); and the Networking Research Center on Bioengineering, Biomaterials, and Nanomedicine (CIBER‐BBN). Part of the characterization work has been performed by the ICTS “NANBIOSIS”, at the Biomaterial Processing and Nanostructuring Unit #6 of the CIBER in Bioengineering, Biomaterials & Nanomedicine (CIBER‐BBN). D.B. and A.A. acknowledge the European Commission (EC) FP7‐PEOPLE‐2013‐Initial Training Networks (ITN) “NANO2FUN” project no. 607721 for their predoctoral contracts. This work was also supported by the Ministero dell'Istruzione, dell'Università e della Ricerca (MIUR; Progetto PRIN 2012 prot. 2012A4Z2RY and Project PON02_00563_3316357 (PON MAAT)). Financial support from the Fonds National Suisse de la Recherche Scientifique (no. 200020‐165890) and the University of Geneva is also acknowledged.
- Published
- 2018
25. Excimers from stable and persistent supramolecular radical-pairs in red/NIR-emitting organic nanoparticles and polymeric films
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Immaculada Ratera, Davide Blasi, Francesca Terenziani, Jaume Veciana, Domna Maria Nikolaidou, European Commission, Dirección General de Investigación Científica y Técnica, DGICT (España), Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España), Generalitat de Catalunya, and Ministerio de Economía y Competitividad (España)
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Materials science ,Luminescence ,Photochemistry ,Triphenylamine ,Supramolecular chemistry ,General Physics and Astronomy ,Nanoparticle ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Arylmethyl radicals ,Fluorescence ,Emission ,chemistry.chemical_compound ,Colloid ,Molecule ,Emission spectrum ,Physical and Theoretical Chemistry ,Temperatures ,Pyrene ,Doping ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Triphenylmethyl radical ,Molecular materials ,Photophysics ,chemistry ,0210 nano-technology - Abstract
In this work, the luminescence properties of new materials based on open-shell molecular systems are studied. In particular, we prepared polymeric films and organic nanoparticles (ONPs) doped with triphenylmethyl radical molecules. ONPs exhibit a uniform size distribution, spherical morphology and high colloidal stability. The emission spectrum of low-doped ONP suspensions and low-doped films is very similar to the emission spectrum of TTM in solution, while the luminescence lifetime and the luminescence quantum yield (LQY) are highly increased. Increasing the radical doping leads to a progressive decrease of the LQY and the appearance of a new broad excimeric band at longer wavelengths, both for ONPs and films. Thus, not only the luminescence properties were improved, but also the formation of excimers from stable and persistent supramolecular radical-pairs was observed for the first time. The good stability and luminescence properties with emission in the red-NIR region (650–800 nm), together with the open-shell nature of the emitter, make these free-radical excimer-forming materials promising candidates for optoelectronic and bioimaging applications., The research leading to these results received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007–2013 under a REA grant agreement no. 607721 (ITN Nano2Fun). A DGI grant (BeWell; CTQ2013-40480-R and Dynamo MAT2013-50036-EXP), the Networking Research Center on Bioengineering, Biomaterials, and Nanomedicine (CIBER-BBN), the Generalitat de Catalunya (grant 2014-SGR-17) are also acknowledged. ICMAB acknowledges support from the Spanish Ministry of Economy and Competitiveness, through the “Severo Ochoa” Programme for Centres of Excellence in R&D (SEV-2015-0496). This work has been developed inside the Materials Science PhD programs of Universitat Autonoma de Barcelona and of University of Parma.
- Published
- 2017
26. Pressure-Induced Conductivity in a Neutral Nonplanar Spin- Localized Radical
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Manuel Souto, Harald Olaf Jeschke, Davide Blasi, Miriam Peña-Alvarez, Imma Ratera, Milan Tomic, Valentín G. Baonza, Concepció Rovira, Jaume Veciana, Roser Valentí, Hengbo Cui, European Commission, Generalitat de Catalunya, Ministerio de Economía y Competitividad (España), and Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España)
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Radical ,Mott insulator ,Intermolecular force ,02 engineering and technology ,General Chemistry ,Conductivity ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,01 natural sciences ,Biochemistry ,Catalysis ,0104 chemical sciences ,chemistry.chemical_compound ,Delocalized electron ,Colloid and Surface Chemistry ,chemistry ,Chemical physics ,Electrical resistivity and conductivity ,Molecule ,0210 nano-technology ,Tetrathiafulvalene - Abstract
Souto, Manuel et al., There is a growing interest in the development of single-component molecular conductors based on neutral organic radicals that are mainly formed by delocalized planar radicals, such as phenalenyl or thiazolyl radicals. However, there are no examples of systems based on nonplanar and spin-localized C-centered radicals exhibiting electrical conductivity due to their large Coulomb energy (U) repulsion and narrow electronic bandwidth (W) that give rise to a Mott insulator behavior. Here we present a new type of nonplanar neutral radical conductor attained by linking a tetrathiafulvalene (TTF) donor unit to a neutral polychlorotriphenylmethyl radical (PTM) with the important feature that the TTF unit enhances the overlap between the radical molecules as a consequence of short intermolecular S···S interactions. This system becomes semiconducting upon the application of high pressure thanks to increased electronic bandwidth and charge reorganization opening the way to develop a new family of neutral radical conductors., This work was supported by the EU ITN iSwitch 642196 DGI grant (BeWell; CTQ2013-40480-R), the Networking Research Center on Bioengineering, Biomaterials, and Nanomedicine (CIBER-BBN), and the Generalitat de Catalunya (grant 2014- SGR-17). This work has also been supported by MINECO through the projects CSD2007-00045, CTQ2012- 38599-C02- 02 and CTQ2013-48252-P. ICMAB acknowledges support from the Spanish Ministry of Economy and Competitiveness, through the “Severo Ochoa” Programme for Centres of Excellence in R&D (SEV- 2015-0496). M.S. is grateful to Spanish Ministerio de Educación, Cultura y Deporte for a FPU grant and he is enrolled in the Material Science Ph.D. program of UAB. D.B. is grateful to the EC ITN Nano2fun grant no607721. M.P.A. is grateful to the Spanish Ministerio de Educación, Cultura y Deporte for an FPU grant. M.P.A. and V.G.B. thank the project CTQ2015-67755-C2-1-R. H.O. Jeschke, M. Tomic and R. Valenti thank the Deutsche Forschungsgemeinschaft (DFG) for funding through grant SFB/TRR49 and Steve Winter for useful discussions. We thank Carlos Goḿ ez-Garcıá (Univ. Valencia) for SQUID measurements as well as Xavier Fontrodona (Univ. Girona) for X-ray diffraction measurements and Mercedes Taravillo (UCM) for the support provided during the high pressure Raman measurements.
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- 2016
27. 1,2,3-Triazole-Diketopyrrolopyrrole Derivatives with Tunable Solubility and Intermolecular Interactions
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Davide Blasi, Francesca Nicoletta, Jaume Veciana, Immaculada Ratera, Nora Ventosa, Eliana Maiorano, Antonio Ardizzone, Angela Punzi, Gianluca M. Farinola, Ministero dell'Istruzione, dell'Università e della Ricerca, Ministerio de Economía y Competitividad (España), Generalitat de Catalunya, and Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España)
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Azides ,Dyes/Pigments ,Chemistry ,Stereochemistry ,Click chemistry ,Conjugation ,Nitrogen heterocycles ,Organic Chemistry ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,European commission ,Physical and Theoretical Chemistry ,0210 nano-technology - Abstract
1,2,3-Triazole rings bearing hydrophobic aliphatic or hydrophilic oligoether chains were easily introduced at the two ends of the conjugated skeleton of bisthiophene–diketopyrrolopyrrole (TDPP) derivatives by simple click cycloaddition reactions. The combination of side chains with different structures and polarities on the triazole rings with the side chains on the N-atoms of the lactam groups of the TDPP moiety enabled the solubility and the solid-state spectroscopic properties of the resulting conjugated molecules to be tuned. Formation of nanostructured aggregates and dependence of their spectroscopic behavior on the substitution pattern were investigated., This work was financially supported by the Ministero dell'Istruzi-one, dell'Università e della Ricerca (MIUR) [Progetto PRIN 2012prot. 2012A4Z2RY”, “Project PON02_00563_3316357 (PONMAAT), and Project PON03PE_00004_1 (PON MAIND)]. Thiswork was also supported by the Dirección General de Investiga-ción y Gestión del Plan Nacional de I+D+i (DGI) of the Ministeriode Ciencia y Tecnología (Spain) (Grant BE-WELL CTQ2013-40480-R), Agència de Gestió d'Ajuts Universitaris i de Recerca(AGAUR), Generalitat de Catalunya (Grant 2014-SGR-17), and theNetworking Research Center on Bioengineering, Biomaterials,and Nanomedicine (CIBER-BBN). D. B. and A. A. acknowledgethe European Commission (EC) FP7-PEOPLE-2013-Initial Train-ing Networks (ITN) (NANO2FUN Project No. 607721) for theirpredoctoral contracts.
- Published
- 2016
28. Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries
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Dino Tonti, Immaculada Ratera, Alvaro Yamil Tesio, Jaume Veciana, Davide Blasi, and Mara Olivares-Marín
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Battery (electricity) ,Tris ,Radical ,LITHIUM OXYGEN BATTERIES ,Físico-Química, Ciencia de los Polímeros, Electroquímica ,Inorganic chemistry ,chemistry.chemical_element ,Nanotechnology ,Electrolyte ,Redox ,Catalysis ,purl.org/becyt/ford/1 [https] ,chemistry.chemical_compound ,ORGANICS RADICAL ,Materials Chemistry ,purl.org/becyt/ford/1.4 [https] ,Oxygen reduction reaction ,Inert ,Metals and Alloys ,Ciencias Químicas ,General Chemistry ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry ,OXYGEN REDUCTION REACTION ,Ceramics and Composites ,Carbon ,CIENCIAS NATURALES Y EXACTAS - Abstract
We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance. Fil: Tesio, Alvaro Yamil. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España Fil: Blasi, D.. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España Fil: Olivares Marín, M.. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España Fil: Ratera, I.. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España Fil: Tonti, D.. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España Fil: Veciana, J.. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España
- Published
- 2015
29. Electrochemical Investigation of Self-Assembling Monolayers toward Ultrasensitive Sensing
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Angelo Tricase, Anna Imbriano, Eleonora Macchia, Rosaria Anna Picca, Davide Blasi, Luisa Torsi, and Paolo Bollella
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30. Surface composition of mixed self-assembled monolayers on Au by infrared attenuated total reflection spectroscopy
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Alessandro Favia, Giuseppe Colafemmina, Davide Blasi, Angela Stefanachi, Gaetano Scamarcio, Angelo Tricase, Luisa Torsi, and Francesco Leonetti
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chemistry.chemical_classification ,Materials science ,Carboxylic acid ,Analytical chemistry ,General Physics and Astronomy ,Protonation ,Self-assembled monolayer ,02 engineering and technology ,Surfaces and Interfaces ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,chemistry.chemical_compound ,chemistry ,Amide ,Attenuated total reflection ,Monolayer ,0210 nano-technology ,Spectroscopy ,Carbodiimide - Abstract
Self-assembled monolayers (SAMs) of N-(2-hydroxyethyl)-3-mercaptopropanamide (NMPA) were synthesized directly on the surface of electron-beam evaporated Au films, starting from 3-mercaptopropionic acid (3MPA) via ethyl-3-(3-dimethylamino-propyl)carbodiimide/N-hydroxysulfosuccinimide sodium salt (EDC/NHSS) coupling with ethanolamine hydrochloride. The influence on the reaction yield of the acidity of EDC/NHSS solutions (pH = 5.6 or 4.8) was assessed by exploiting the high surface sensitivity of infrared attenuated total reflection spectroscopy. The light-matter interaction was modeled in the framework of a matrix formalism considering the complete multi-layer sample structure. A comparison between the relative intensity of the main absorption bands, associated with amide I and carbonyl stretching of carboxylic acid or amide II vibrations, with a calibration curve obtained from the measurement of mixed 3MPA/NMPA SAMs, show that the more acid solution is 16% more efficient. This is mostly due to the higher protonation of the 3MPA.
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