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1.
Chem Rec ; 23(8): e202200302, 2023 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-37129563

RESUMEN

In the current era that it is strongly expected the SDGs would be achieved, electrolyte solutions in electrochemical devices and processes are being studied from dilute and concentrated solutions, through inorganic molten salts, deep eutectic solvents, and ionic liquids, to super-concentrated solutions. Although concepts based on empirical laws such as the Walden rule and hydrodynamics such as the Stokes rule are still useful for ionic conduction in solution, it is expected that superionic conduction-like mechanisms that are scarcely found in conventional electrolytes. Here, the authors' recent results are described based on the local structure and speciation of ionic species in solution, focusing on protons and lithium ions.

2.
Int J Mol Sci ; 23(1)2022 Jan 03.
Artículo en Inglés | MEDLINE | ID: mdl-35008932

RESUMEN

Amyloid beta peptides (Aßs) are generated from amyloid precursor protein (APP) through multiple cleavage steps mediated by γ-secretase, including endoproteolysis and carboxypeptidase-like trimming. The generation of neurotoxic Aß42/43 species is enhanced by familial Alzheimer's disease (FAD) mutations within the catalytic subunit of γ-secretase, presenilin 1 (PS1). FAD mutations of PS1 cause partial loss-of-function and decrease the cleavage activity. Activating mutations, which have the opposite effect of FAD mutations, are important for studying Aß production. Aph1 is a regulatory subunit of γ-secretase; it is presumed to function as a scaffold of the complex. In this study, we identified Aph1 mutations that are active in the absence of nicastrin (NCT) using a yeast γ-secretase assay. We analyzed these Aph1 mutations in the presence of NCT; we found that the L30F/T164A mutation is activating. When introduced in mouse embryonic fibroblasts, the mutation enhanced cleavage. The Aph1 mutants produced more short and long Aßs than did the wild-type Aph1, without an apparent modulatory function. The mutants did not change the amount of γ-secretase complex, suggesting that L30F/T164A enhances catalytic activity. Our results provide insights into the regulatory function of Aph1 in γ-secretase activity.


Asunto(s)
Secretasas de la Proteína Precursora del Amiloide/metabolismo , Péptidos beta-Amiloides/metabolismo , Endopeptidasas/genética , Glicoproteínas de Membrana/metabolismo , Proteínas de la Membrana/genética , Mutación , Enfermedad de Alzheimer/etiología , Enfermedad de Alzheimer/genética , Enfermedad de Alzheimer/metabolismo , Precursor de Proteína beta-Amiloide/metabolismo , Animales , Dominio Catalítico , Endopeptidasas/metabolismo , Fibroblastos/metabolismo , Humanos , Proteínas de la Membrana/metabolismo , Ratones , Presenilina-1/metabolismo , Proteolisis , Saccharomyces cerevisiae
3.
Angew Chem Int Ed Engl ; 55(21): 6266-9, 2016 05 17.
Artículo en Inglés | MEDLINE | ID: mdl-27071502

RESUMEN

To quantify the properties of protic ionic liquids (PILs) as acid-base reaction media, potentiometric titrations were carried out in a neat PIL, ethylammonium nitrate (EAN). A linear relationship was found between the 14 pKa  values of 12 compounds in EAN and in water. In other words, the pKa  value in EAN was found to be roughly one unit greater than that in water regardless of the charge and hydrophobicity of the compounds. It is possible that this could be explained by the stronger acidity of HNO3 in EAN than that of H3 O(+) in water and not by the difference in the solvation state of the ions. The pH value in EAN ranges from -1 to 9 on the pH scale based on the pH value in water.

4.
Environ Pollut ; 355: 124195, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-38776998

RESUMEN

The respiratory effects of particulate matter (PM) in subway station platforms or tunnels have attracted considerable research attention. However, no studies have characterized the effects of subway PM on allergic immune responses. In this study, iron oxide (α-Fe2O3 and Fe3O4) particles-the main components of subway PM-were intratracheally administered to BALB/c mice where ovalbumin (OVA) induced allergic pulmonary inflammation. Iron oxide particles enhanced OVA-induced eosinophil recruitment around the bronchi and mucus production from airway epithelium. The concentrations of type 2 cytokines, namely, interleukin (IL)-5 and IL-13, in bronchial alveolar lavage fluids were increased by iron oxide particles. Iron oxide particles also increased the number of type 2 innate lymphoid cells and CD86+ cells in the lung. Moreover, phagocytosis of particles in lung cells was confirmed by Raman spectroscopy. In a subsequent in vitro study, bone marrow-derived antigen-presenting cells (APCs) isolated from NC/Nga mice were exposed to iron oxide particles and OVA. They were also exposed to outdoor ambient PM: Vehicle Exhaust Particulates (VEP) and Urban Aerosols (UA) as references. Iron oxide particles promoted the release of lactate dehydrogenase, C-X-C motif chemokine ligand 1 and IL-1α from APCs, which tended to be stronger than those of VEP. These results suggest that iron oxide particles enhance antigen presentation in the lungs, promoting allergic immune response in mice; iron oxide particles-induced death and inflammatory response of APCs can contribute to allergy exacerbation. Although iron oxide particles do not contain various compounds like VEP, iron oxide alone may have sufficient influence.


Asunto(s)
Contaminantes Atmosféricos , Compuestos Férricos , Hipersensibilidad , Ratones Endogámicos BALB C , Material Particulado , Animales , Material Particulado/toxicidad , Ratones , Contaminantes Atmosféricos/toxicidad , Hipersensibilidad/inmunología , Pulmón/efectos de los fármacos , Pulmón/inmunología , Citocinas/metabolismo , Ovalbúmina , Líquido del Lavado Bronquioalveolar/química , Emisiones de Vehículos/toxicidad , Femenino
5.
Phys Chem Chem Phys ; 15(39): 16956-64, 2013 Oct 21.
Artículo en Inglés | MEDLINE | ID: mdl-24002168

RESUMEN

Human calcitonin (hCT) is a 32-amino acid peptide hormone that contains an intrachain disulfide bridge between Cys1 and Cys7 and a proline amide at the C-terminus. hCT tends to associate to form a fibril precipitate of the same type as amyloid fibrils, and hence has been studied as a model of amyloid fibril formation. The fibrillation process in N-(2-hydroxyethyl)piperazine-N'-2-ethanesulfonic acid (HEPES) solution was examined using transmission electron microscopy. The rate of hCT fibrillation in HEPES solution was much lower than in phosphate buffer and acetic acid solution. Spherical intermediate aggregates (nuclei) were observed during the early stage of fibril formation. Short proto-fibrils appeared on the surface of the spherical intermediates. Subsequently, the spherical intermediates transformed directly into long proto-fibrils, which then elongated into mature hCT fibrils. The fibrillation process was also examined using solid-state (13)C-NMR spectroscopy, which indicated that the fibril structure was a ß-sheet in the central region and a mixture of random coils and ß-sheets at the C-terminus. The kinetics of fibril formation was examined in terms of a two-step autocatalytic reaction mechanism. The first-step nucleation rate (k1) was lower in HEPES solution than in phosphate buffer and acetic acid solution because the half-life of the intermediates is significantly longer in HEPES solution. In contrast, the second-step fibril elongation rate (k2) was similar in HEPES solution and acidic solutions. Specific interaction of HEPES molecules with hCT may stabilize the spherical intermediates and consequently inhibit the fibril elongation process of hCT.


Asunto(s)
Calcitonina/química , Espectroscopía de Resonancia Magnética , Microscopía Electrónica de Transmisión , Fragmentos de Péptidos/química , Secuencia de Aminoácidos , Péptidos de Penetración Celular , HEPES , Humanos , Concentración de Iones de Hidrógeno , Datos de Secuencia Molecular , Estructura Molecular , Estructura Secundaria de Proteína , Soluciones
6.
Phys Chem Chem Phys ; 15(23): 8890-901, 2013 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-23552643

RESUMEN

Calcitonin (CT) is an amyloid fibril forming peptide. Since salmon calcitonin (sCT), having Leu residues (Leu12, Leu16 or Leu19) instead of Tyr12, Phe16 or Phe19 for human calcitonin (hCT), is known to form the fibrils much slower than hCT, hCTs mutated to Leu residues at the position of 16 (F16L-hCT), 19 (F19L-hCT), and 12, 16 and 19 (TL-hCT) were examined to reveal the role of aromatic side-chains on amyloid fibrillation using solid-state (13)C NMR. The detailed kinetics were analyzed using a two-step reaction mechanism such as nucleation and fibril elongation with the rate constants of k1 and k2, respectively. The k2 values of hCT mutants were significantly slower than that of hCT at a neutral pH, although they were almost the same at an acidic pH. The (13)C chemical shifts of the labeled sites showed that the conformations of monomeric hCT mutants take α-helices as viewed from the Gly10 moiety. The hCT mutants formed fibrils and during the fibril formation, the α-helix around Gly10-Phe22 changed to the ß-sheet, and the major structures around Ala26-Ala31 were random coil in the fibrils. Molecular dynamics simulation was performed for the ß-sheet system of hCT9-23 and its mutants F16L-hCT9-23, F19L-hCT9-23 and TL-hCT9-23. In one of the stable fibril structures, Phe16 of hCT interacts with Phe19 of the next strand alternatively. In the hCT mutants, lack of Phe16 and Phe19 interaction causes significant instability as compared with the hCT fibril, leading to the reduction of k2 values, as observed experimentally in the hCT mutants at a neutral pH.


Asunto(s)
Amiloide/química , Amiloide/metabolismo , Calcitonina/química , Calcitonina/metabolismo , Amiloide/genética , Amiloide/ultraestructura , Calcitonina/genética , Humanos , Simulación de Dinámica Molecular , Resonancia Magnética Nuclear Biomolecular , Mutación Puntual , Estructura Secundaria de Proteína
7.
Anal Sci ; 39(2): 133-137, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-36653697

RESUMEN

Analytical Chemistry, through quantitative and/or qualitative analysis (identification), is a discipline that involves the development of methodologies and the exploration of new principles to obtain answers to given problems. In situ analysis techniques have attracted attention for its ability to elucidate phenomena occurring and to evaluate amount of a certain component in substances at real time and biological samples as applications of such analysis technology. Lots of techniques have been performed to understand the fundamental phenomena in varied fields such as X-ray, vibrational, and electrochemical impedance spectroscopies and also analytical reagents that enable to semi-quantitative analysis just observation. In fact, applying various in situ techniques in analytical chemistry expands to the medical diagnosis, which leads to be able to detect early diseases. Here, we describe some of previous researches in many fields such as electrochemical device for energy storage, biology, environment, and pathology and briefly introduce our recent challenges to analytical chemistry toward the on-site diagnosis.

8.
Biosens Bioelectron ; 238: 115555, 2023 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-37542977

RESUMEN

Acetaldehyde, which is an intermediate product of alcohol metabolism, is known to induce symptoms, including alcohol flushing, vomiting, and headaches in humans. Therefore, real-time monitoring of acetaldehyde levels is crucial to mitigating these health issues. However, current methods for detecting low-concentration gases necessitate the use of complex measurement equipment. In this study, we developed a low-cost, low-detection-limit, enzyme-based electrochemical biosensor for acetaldehyde gas detection that does not require sophisticated equipment. The sensor was constructed by screen-printing electrodes onto a porous polyimide film, using grafted MgO-templated carbon (GMgOC) as working electrode material, carbon for the counter electrode, and silver/silver chloride for the reference electrode. Pyrroloquinoline-quinone-dependent aldehyde dehydrogenase was immobilized on the working electrode, and a chamber was attached to the electrode chip and filled with 1-methoxy-5-methylphenazinium methyl sulfate solution. The sensor can be used to measure acetaldehyde gas concentrations from 0.02 to 0.1 ppm, making it suitable for monitoring human skin gas. This low detection limit was achieved by delivering the analyte through the porous polyimide film on which the electrodes were printed and accumulating acetaldehyde in the mesoporous GMgOC of the working electrode. This mechanism suggests that this sensor design can be adapted to develop other low-detection limit gas sensors, such as those for screening skin gas biomarkers.


Asunto(s)
Técnicas Biosensibles , Carbono , Humanos , Técnicas Biosensibles/métodos , Acetaldehído , Porosidad , Electrodos
9.
ACS Sens ; 8(7): 2889-2895, 2023 07 28.
Artículo en Inglés | MEDLINE | ID: mdl-37318827

RESUMEN

Wearable ion sensors for the real-time monitoring of sweat biomarkers have recently attracted increasing research attention. Here, we fabricated a novel chloride ion sensor for real-time sweat monitoring. The printed sensor was heat-transferred onto nonwoven cloth, allowing for easy attachment to various types of clothing, including simple garments. Additionally, the cloth prevents contact between the skin and the sensor and acts as a flow path. The change in the electromotive force of the chloride ion sensor was -59.5 mTV/log CCl-. In addition, the sensor showed a good linear relationship with the concentration range of chloride ions in human sweat. Moreover, the sensor displayed a Nernst response, confirming no changes in the film composition due to heat transfer. Finally, the fabricated ion sensors were applied to the skin of a human volunteer subjected to an exercise test. In addition, a wireless transmitter was combined with the sensor to wirelessly monitor ions in sweat. The sensors showed significant responses to both sweat perspiration and exercise intensity. Thus, our research demonstrates the potential of using wearable ion sensors for the real-time monitoring of sweat biomarkers, which could significantly impact the development of personalized healthcare.


Asunto(s)
Sudor , Dispositivos Electrónicos Vestibles , Humanos , Cloruros , Calor , Biomarcadores , Impresión Tridimensional
10.
ACS Sens ; 8(6): 2368-2374, 2023 06 23.
Artículo en Inglés | MEDLINE | ID: mdl-37216270

RESUMEN

This study aimed to develop a lactate sensor with a microchannel that overcomes the issue of air bubbles interfering with the measurement of lactate levels in sweat and to evaluate its potential for continuous monitoring of lactate in sweat. To achieve continuous monitoring of lactate, a microchannel was used to supply and drain sweat from the electrodes of the lactate sensor. A lactate sensor was then developed with a microchannel that has an area specifically designed to trap air bubbles and prevent them from contacting the electrode. The sensor was evaluated by a person while exercising to test its effectiveness in monitoring lactate in sweat and its correlation with blood lactate levels. Furthermore, the lactate sensor with a microchannel in this study can be worn on the body for a long time and is expected to be used for the continuous monitoring of lactate in sweat. The developed lactate sensor with a microchannel effectively prevented air bubbles from interfering with the measurement of lactate levels in sweat. The sensor showed a concentration correlation ranging from 1 to 50 mM and demonstrated a correlation between lactate in sweat and blood. Additionally, the lactate sensor with a microchannel in this study can be worn on the body for an extended period and is expected to be useful for the continuous monitoring of lactate in sweat, particularly in the fields of medicine and sports.


Asunto(s)
Técnicas Biosensibles , Ácido Láctico , Humanos , Sudor , Microfluídica , Electrodos
11.
Anal Sci ; 38(8): 1025-1031, 2022 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-35672500

RESUMEN

Isotopic H/D or 6/7Li substitution Raman spectroscopy was applied to new kinds of ionic liquids; N-methylimidazole (C1Im) and acetic acid (CH3COOH) as the pseudo-protic ionic liquid (pPIL), and both of the neat and the 2,2,3,3-tetrafluoropropyl ether (HFE) diluted Li-glyme solvate ionic liquids (SIL) [Li(Gn)][TFSA] (Gn, glyme n = 3 or 4); TFSA, bis(trifluoromethanesulfonyl)amide) to clarify the proton transfer or the Li+ solvation/ion pair formation. The isotopic substitution Raman (ISR) spectra were obtained as the difference between the samples containing the same composition except the substituted isotope. The calculated and theoretical ISR spectra were also evaluated for comparison. With the C1Im-CH3COOH(D) pPIL, the Raman bands attributable to the C1Im/C1HIm+ gave signals of differential shape, and they were well reproduced with the curve fitting by taking the small amount of C1HIm+ and CH3COO- generation into consideration. The ISR spectra for the SIL were well explained by the formation of the Li-TFSA contact ion pair (CIP) and the solvent shared ion pair (SSIP) in the [Li(G3)][TFSA] SIL. In addition, the ISR spectra for the HFE-diluted [Li(G4)][TFSA] SIL clearly proved that the HFE hardly coordinates to the Li+ in the HFE-diluted SIL. Here, the ISR spectroscopy is proposed as a new tool for studying the ion solvation and the ion pair formation in ionic liquids.

12.
Sci Rep ; 12(1): 14649, 2022 08 27.
Artículo en Inglés | MEDLINE | ID: mdl-36030337

RESUMEN

In this study, the performance of a paper-based, screen-printed biofuel cell with mesoporous MgO-templated carbon (MgOC) electrodes was improved in two steps. First, a small amount of carboxymethyl cellulose (CMC) was added to the MgOC ink. Next, the cathode was modified with bilirubin prior to immobilizing the bilirubin oxidase (BOD). The CMC increased the accessibility of the mesopores of the MgOC, and subsequently, the performance of both the bioanode and biocathode. CMC also likely increased the stability of the electrodes. The pre-modification with bilirubin improved the orientation of the BOD, which facilitated direct electron transfer. With these two steps, an open circuit potential of 0.65 V, a maximal current density of 1.94 mA cm-2, and a maximal power density of 465 µW cm-2 was achieved with lactate oxidase as bioanode enzyme and lactate as fuel. This is one of the highest reported performances for a biofuel cell.


Asunto(s)
Fuentes de Energía Bioeléctrica , Carbono , Bilirrubina , Electrodos , Enzimas Inmovilizadas , Glucosa , Tinta , Oxidorreductasas actuantes sobre Donantes de Grupo CH-CH
13.
J Exp Psychol Anim Learn Cogn ; 47(3): 274-280, 2021 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-34618527

RESUMEN

We have previously demonstrated that chimpanzees, similar to humans, can discriminate the orientations of a diagonal line better when lines are presented in redundant contexts than alone. In the present study, we examined whether the same redundant context facilitated diagonal-orientation discrimination in mice. Mice were presented one of three simultaneous, diagonal-orientation discrimination tasks: (a) presented alone, (b) presented with the context that resulted in emergent configurations in chimpanzees and humans, and (c) presented with the context not resulting in emergent configurations in chimpanzees or humans. In contrast to the facilitative effect of congruent context in chimpanzees and humans, the identical context did not facilitate the discrimination of the diagonal orientation in mice. This finding suggests that mice, unlike chimpanzees and humans, do not perceive emergent Gestalt. (PsycInfo Database Record (c) 2021 APA, all rights reserved).


Asunto(s)
Pan troglodytes , Animales , Ratones
14.
RSC Adv ; 11(33): 20550-20556, 2021 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-35479878

RESUMEN

In this study, magnesium oxide (MgO)-templated mesoporous carbon (MgOC) and chitosan cross-linked with genipin (chitosan-genipin) were considered bio-composite inks for screen-printed bioanodes. The fabrication processes were optimized using rheological and structural data, and a bioanode ink containing glucose oxidase (GOx) and 1,2-naphthoquinone (1,2-NQ) was successfully developed. The optimal bioanode-ink contained MgOC pre-treated by washing to achieve a hydrophilic and neutral surface, which helped maintain enzyme activity and resulted in a highly porous electrode structure, which is essential for the accessibility of glucose to GOx. A bioanode fabricated using this ink showed a linear response current dependency up to 8 mM glucose with a sensitivity of 25.83 µA cm-2 mM-1. Combined with a conventional biocathode, an electromotive force of 0.54 V and a maximal power density of 96 µW cm-2 were achieved. These results show that this bio-composite ink can be used to replace the multi-step process of printing with conventional ink followed by drop-casting enzyme and mediator with a one-step printing process.

15.
Nagoya J Med Sci ; 83(1): 41-49, 2021 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-33727736

RESUMEN

The effects of pregnancy on balance with the eyes closed and maximum walking speed remain unclarified. The present study aimed to examine the effect of simulated gestational weight gain on balance, gait, and fear of falling in nulligravid women to enhance understanding of the impact of gestational weight gain. We prospectively evaluated the following outcomes in 24 healthy nulligravid women with and without a maternity-simulation jacket that simulated third-trimester pregnancy. To measure balance, we used the single-leg-stance test with eyes open and closed, and the functional reach test. We evaluated gait function by measuring walking speed, step length, and cadence at self-selected and maximum speeds. We used the timed-up-and-go test as a comprehensive measure of gait and balance, and the modified falls efficacy scale to evaluate fear of falling. Differences in these parameters between a simulated gestational weight gain condition and a "nonpregnant" condition were assessed. Simulated gestational weight gain caused significantly worse performances in the single-leg-stance test with eyes open and closed, functional reach test, walking speed, step length at self-selected and maximum speeds, and timed-up-and-go test. The effect size was larger for the single-leg-stance test with eyes closed than with eyes open. The average score for each modified falls efficacy scale item ranged from 4.7-8.5. In conclusion, balance decreased with simulated gestational weight gain, and balance may be more affected without visual feedback. Simulated gestational weight gain resulted in worse gait function at both self-selected and maximum speeds.


Asunto(s)
Miedo , Ganancia de Peso Gestacional/fisiología , Equilibrio Postural , Embarazo/fisiología , Velocidad al Caminar , Accidentes por Caídas , Prueba de Esfuerzo , Femenino , Análisis de la Marcha , Humanos , Simulación de Paciente , Tercer Trimestre del Embarazo , Estudios Prospectivos , Escalas de Valoración Psiquiátrica , Adulto Joven
16.
J Phys Chem B ; 125(27): 7477-7484, 2021 07 15.
Artículo en Inglés | MEDLINE | ID: mdl-34196549

RESUMEN

It has been reported that aqueous lithium ion batteries (ALIBs) can operate beyond the electrochemical window of water by using a superconcentrated electrolyte aqueous solution. The liquid structure, particularly the local structure of the Li+, which is rather different from conventional dilute solution, plays a crucial role in realizing the ALIB. To reveal the local structure around Li+, the superconcentrated LiTFSA (TFSA: bis(trifluoromethylsulfonil)amide) aqueous solutions were investigated by means of Raman spectroscopic experiments, high-energy X-ray total scattering measurements, and the neutron diffraction technique with different isotopic composition ratios of 6Li/7Li and H/D. The Li+ local structure changes with the increase of the LiTFSA concentration; the oligomer ([Lip(TFSA)q](p-q)+ (q > 2) forms at the molar fraction of LiTFSA (xLiTFSA) > 0.25. The average structure can be determined in which two water molecules and two oxygen atoms of TFSA anion(s) coordinate to the Li+ in the superconcentrated LiTFSA aqueous solution (LiTFSA)0.25(H2O)0.75. In addition, the intermolecular interaction between the neighboring water molecules was not found, and the hydrogen-bonded interaction in the solution should be significantly weak. According to the coordination number of the oxygen atom (TFSA or H2O), a variety of TFSA- and H2O coordination manners would exist in this solution; in particular, the oligomer is formed in which the monodentate TFSA cross-links Li+.


Asunto(s)
Litio , Agua , Iones , Difracción de Neutrones , Espectrometría Raman
17.
J Phys Chem B ; 124(49): 11157-11164, 2020 12 10.
Artículo en Inglés | MEDLINE | ID: mdl-33198463

RESUMEN

To clarify proton conduction mechanism in protic ionic liquids (PILs) and pseudo-PILs (pPILs), equimolar mixtures of N-methylimidazole (C1Im) with fluorinated acetic acids were investigated by Raman spectroscopy, X-ray scattering, and dielectric relaxation spectroscopy (DRS). Only the ionic species exist in the equimolar mixture of C1Im and HTFA (HTFA: trifluoroacetic acid). On the other hand, the equimolar mixture of C1Im and HDFA (HDFA: difluoroacetic acid) consists of both ionic and electrically neutral species. In particular, not only the electrostatic but also van der Waals interactions with the F atoms were observed in the liquid structures of both [C1hIm+][TFA-] and [C1hIm+][DFA-]. The concept for proton conduction mechanism that we have proposed in previous study was revisited; the proton conduction mechanism could be classified with two linear free energy relationship lines for proton exchange reaction and translation/rotation of proton carriers. Our results exhibit that the proton conduction mechanism changes from proton hopping to vehicle mechanism with increasing acidity of an acid HA in PILs.

18.
J Phys Chem Lett ; 11(11): 4517-4523, 2020 Jun 04.
Artículo en Inglés | MEDLINE | ID: mdl-32338919

RESUMEN

Lithium-glyme solvated ionic liquids (Li-G SILs) and superconcentrated electrolyte solutions (SCESs) are expected to be promising electrolytes for next-generation lithium secondary batteries. The former consists of only the oligoether glyme solvated lithium ion and its counteranion, and the latter contains no full solvated Li+ ion by the solvents due to the extremely high Li salt concentration. Although both of them are similar to each other, it is still unclear that both should be room-temperature ionic liquids. To distinctly define them, speciation analyses were performed with the Li-G SIL and the aqueous SCES to evaluate the free solvent concentration in these solutions with a new Raman/infrared spectral analysis technique called complementary least-squares analysis. Furthermore, from a thermodynamic point of view, we investigated the solvent activity and activity coefficient in the gas phase equilibrated with sample solutions and found they can be good criteria for SILs.

19.
J Phys Chem B ; 124(46): 10456-10464, 2020 11 19.
Artículo en Inglés | MEDLINE | ID: mdl-33161707

RESUMEN

Neutron diffraction measurements on 6Li/7Li isotopically substituted 10 and 33 mol % *LiTFSA (lithium bis(trifluoromethylsulfonyl)amide)-AN-d3 (acetonitrile-d3) and 10 and 33 mol % *LiTFSA-DMF-d7(N,N-dimethylformamide-d7) solutions have been carried out in order to obtain structural insights on the first solvation shell of Li+ in highly concentrated organic solutions. Structural parameters concerning the local structure around Li+ have been determined from the least squares fitting analysis of the first-order difference function derived from the difference between carefully normalized scattering cross sections observed for 6Li-enriched and natural abundance solutions. In 10 mol % LiTFSA-AN-d3 solution, 3.25 ± 0.04 AN molecules are coordinated to Li+ with a intermolecular Li+···N(AN) distance of 2.051 ± 0.007 Å. It has been revealed that 1.67 ± 0.07 AN molecules and 2.00 ± 0.01 TFSA- are involved in the first solvation shell of Li+ in the 33 mol % LiTFSA-AN solution. The nearest neighbor Li+···NAN and Li+···OTFSA- distances are obtained to be r(Li+···N) = 2.09 ± 0.01 Å and r(Li+···O) = 1.88 ± 0.01 Å, respectively. The first solvation shell of Li+ in the 10 mol % LiTFSA-DMF-d7 solutions contains 3.4 ± 0.1 DMF molecules with an intermolecular Li+···ODMF distance of 1.95 ± 0.02 Å. In highly concentrated 33 mol % LiTFSA-DMF-d7 solutions, there are 1.3 ± 0.2 DMF molecules and 3.2 ± 0.2 TFSA- in the first solvation shell of Li+ with intermolecular distances of r(Li+···ODMF) = 1.90 ± 0.02 Å and r(Li+···OTFSA-) = 2.01 ± 0.01 Å, respectively. The Li+···TFSA- contact ion pair stably exists in highly concentrated 33 mol % LiTFSA-AN and -DMF solutions.

20.
J Phys Chem B ; 123(29): 6244-6252, 2019 Jul 25.
Artículo en Inglés | MEDLINE | ID: mdl-31251059

RESUMEN

In a previous work, we have found that the pseudo-protic ionic liquid N-methylimidazolium acetate, [C1HIm][OAc] or [Hmim][OAc], mainly consists of the electrically neutral molecular species N-methylimidazole, C1Im, and acetic acid, AcOH, even though the mixture has significant ionic conductivity. This system was revisited by employing isotopic substitution Raman spectroscopy (ISRS) and pulsed field gradient (PFG) NMR self-diffusion measurements. The ISRS and PFG-NMR results obtained fully confirm our earlier findings. In particular, the self-diffusion coefficient of the hydroxyl hydrogen atom in AcOH is identical to that of the methyl hydrogen atoms within the experimental uncertainty, consistent with very little ionization. Therefore, a proton conduction mechanism similar to the Grotthuss mechanism for aqueous acid solutions is postulated to be responsible for the observed electrical conductivity. Laity resistance coefficients (rij) are calculated from the transport properties, and the negative values obtained for the like-ion interactions are consistent with the pseudo-ionic liquid description, that is, the mixture is indeed a very weak electrolyte. The structure and rotational dynamics of the mixture were also investigated using high-energy X-ray total scattering experiments, molecular dynamics simulations, and dielectric relaxation spectroscopy. Based on a comparison of activation energies and the well-known linear free energy relationship between the kinetics and thermodynamics of autoprotolysis, we propose for [C1HIm][OAc] a Grotthus-type proton conduction mechanism involving fast AcOH/AcO- rotation as a decisive step.

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