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1.
Exploration (Beijing) ; 4(3): 20230040, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38939863

RESUMO

Molecular hydrogen (H2) ortho-para conversion (O/P conversion) proceeds slowly at low temperatures accompanying a heat release. Thus, catalysts for accelerating this conversion rate are highly demanded in terms of the storage and utilization of liquid H2. The catalysts for this purpose are experimentally screened by examining a broad range of materials covering magnetic, non-magnetic, metallic, and nonmetallic oxides. The primary conclusions obtained are summarized below. (1) active materials are required to be non-metallic and to bear the cations with ionic radii smaller than the bond length of H2. (2) Metallic materials have almost no activity irrespective of with or without magnetism (3) The activity of materials belonging to (1) is largely enhanced when the constituting cation has a magnetic moment. In addition, there is a class of materials for which the activity is distinctly enhanced just upon substitution by the foreign ions.

2.
Chem Senses ; 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38771102

RESUMO

Toxic puffers accumulate tetrodotoxin (TTX), a well-known neurotoxin, by feeding on TTX-bearing organisms and using it to defend themselves from predators. Our previous studies have demonstrated that toxic puffers are attracted to 5,6,11-trideoxytetrodotoxin (TDT), a nontoxic TTX analog that is simultaneously accumulated with TTX in toxic puffers and their prey. In addition, activity labeling using immunohistochemistry targeting neuronal activity marker suggests that TDT activates crypt olfactory sensory neurons (OSN) of the green spotted puffer. However, it remains to be determined whether individual crypt OSNs can physiologically respond to TDT. By employing electroporation to express GCaMP6s in OSNs, we successfully identified a distinct group of oval OSNs that exhibited a specific calcium response when exposed to TDT in green spotted puffers. These oval OSNs showed no response to amino acids (AAs), which serve as food odor cues for teleosts. Furthermore, oval morphology and surface positioning of TDT-sensitive OSNs in the olfactory epithelium closely resemble that of crypt OSNs. These findings suggest that TDT is specifically detected by crypt OSNs in green spotted puffer. The TDT odor may act as a chemoattractant for finding conspecific toxic puffers and for feeding TTX-bearing organisms for effective toxification.

3.
Nanoscale Adv ; 6(10): 2582-2585, 2024 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-38752141

RESUMO

A novel patterning method achieves two-dimensional nano-patterning of metal nanofibers by depositing a platinum-cerium alloy film on a silicon wafer and inducing phase separation in an oxygen-carbon monoxide atmosphere. The resulting nano-patterned thin film, Pt#CeO2/Si, consists of platinum and cerium oxide with an average pattern width of 50 nm and exhibits potential as a hydrogen sensor with sensitive electrical responses to hydrogen ad/desorption. The patterning method introduced herein addresses the challenge of wavelength limitations in traditional optical lithography, offering a scalable approach for sub-50 nm patterns, which are crucial for advanced sensor and electronic applications.

4.
RSC Adv ; 14(24): 17213-17217, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38812960

RESUMO

Site-targeted decoration of catalytic nanocrystals is essential for maximizing performance with minimal materials use. Here, we demonstrate successful, site-targeted decoration of palladium (Pd) nanocrystals with nickel (Ni) exclusively along crystal facet edges through the thermal decomposition of nickel carbonyl (Ni(CO)4) vapor. Strong interactions between carbon monoxide and Pd facet for passivation or between Ni(CO)4 and crystal facet edges resulted in selective Ni decoration at the nanocrystal edges. The Ni-decorated Pd nanocrystals exhibit superior catalytic performance for methane (CH4) removal in an oxygen-rich lean-burn exhaust atmosphere, requiring 10 times less Ni decoration than conventional Pd-Ni composite catalysts prepared by the wet impregnation method. The site-targeted decoration of nanocrystals introduced in this work offers an efficient and resource-minimizing strategy for enhanced catalytic applications.

5.
Phys Chem Chem Phys ; 26(19): 14103-14107, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38695831

RESUMO

Metal-oxide nanocomposites (MONs) are of pivotal importance as electrode materials, yet lack a guiding principle to tune their phase texture. Here we report that the phase texture of MONs can be tuned at the nanoscale by controlling the nanophase separation of precursor alloys. In situ transmission electron microscopy (in situ TEM) has demonstrated that a MON material of platinum (Pt) and cerium oxide (CeO2) is obtained through promoted nanophase separation of a Pt5Ce precursor alloy in an atmosphere containing oxygen (O2) and carbon monoxide (CO). The Pt-CeO2 MON material comprised an alternating stack of nanometre-thick layers of Pt and CeO2 in different phase textures ranging from lamellae to mazes, depending on the O2 fraction in the atmosphere. Mathematical simulations have demonstrated that the phase texture of MONs originates from a balance in the atomic diffusions across the alloy precursor, which is controllable by the O2 fraction, temperature, and composition of the precursor alloys.

6.
Sci Total Environ ; 931: 172401, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38677413

RESUMO

To understand the differences in degradation processes depending on the chemical properties of polymers, it is necessary to both quantify the microbiome composition and evaluate the process of microbial turnover (i.e., community assembly processes) in a variety of polymer materials. In this study, using a phylogenetic bin-based null model analysis (i.e., iCAMP), we evaluated community assembly processes from original estuary water to 37 types of polymers, which provide overwhelmingly diverse niches for microbes, in 14-day incubation experiments. First, we evaluated the polymer properties related to degradation rates. Polymers with higher adipic acid (AdA) monomer exhibited higher motility, hydrophilicity, and degradation rates, whereas those with higher aromatic monomer exhibited the opposite trends. Second, microbiome composition analysis was performed, and the microbiomes were significantly changed by the AdA or aromatic content. This was consistent with the polymer properties, suggesting that polymer motility and hydrophilicity attributable to the first-order structure modify the accessibility of the enzyme to the reaction site and hence the degradation rate, resulting in differences in microbiome community composition. Finally, we determined community assembly processes from estuary water to plastics using a phylogenetic bin-based null model analysis. The importance of heterogeneous selection was higher in mobile, hydrophilic, and fast-degrading polymers, while that of homogeneous selection was lower. This suggests that the environmental difference between before and after incubation becomes significant under rapid degradation, which select microbes adapted to biofilm environments. In addition, the more stochastic turnover prevailed, the more variation in the communities (i.e., ß-diversity) increased. This suggests that turnover processes not dictated by the environment lead to instability in community compositions.


Assuntos
Biodegradação Ambiental , Microbiota , Filogenia , Poluentes Químicos da Água/análise , Polímeros , Estuários , Microbiologia da Água
7.
Biomacromolecules ; 25(1): 444-454, 2024 01 08.
Artigo em Inglês | MEDLINE | ID: mdl-38135668

RESUMO

Polyhydroxyalkanoates (PHAs), aliphatic polyesters synthesized by microorganisms, have gained considerable attention as biodegradable plastics. Recently, α-carbon-methylated PHAs have been shown to exhibit several interesting properties that differ from those of conventional PHAs, such as their crystallization behavior and material properties. This study investigated α-carbon methylated (S)- and (R)-3-hydroxy-2-methylpropionate (3H2MP) as new repeating units. 3H2MP units were homopolymerized or copolymerized with (R)-3-hydroxybutyrate (3HB) by manipulating the culture conditions of recombinant Escherichia coli LSBJ. Consequently, PHAs with 3H2MP units ranging from 5 to 100 mol % were synthesized by external addition of (R)- and (S)-enantiomers or the racemic form of 3H2MPNa. The (S)-3H2MP precursor supplemented into the culture medium was almost directly polymerized into PHA while maintaining its chirality. Therefore, a highly isotactic P(3H2MP) (R:S = 1:99) was synthesized, which displayed a melting temperature of 114-119 °C and a relatively high enthalpy of fusion (68 J/g). In contrast, in cultures supplemented with (R)-3H2MP, the precursor was racemized and polymerized into PHA, resulting in the synthesis of the amorphous polymer atactic P(3H2MP) (R:S = 40:60). However, racemization was not observed at a low concentration of the (R)-3H2MP precursor, thereby synthesizing P(3HB-co-8 mol % 3H2MP) with 100% (R)-3H2MP units. The thermogravimetric analysis revealed that the thermal degradation temperatures at 5% weight loss of P(3H2MP)s occurred at approximately 313 °C, independent of tacticity, which is substantially higher than that of P(3HB) (257 °C). This study demonstrates a new concept for controlling the physical properties of biosynthesized PHA by manipulating the polymers' tacticity using 3H2MP units.


Assuntos
Poli-Hidroxialcanoatos , Poli-Hidroxialcanoatos/química , Poliésteres/metabolismo , Hidroxibutiratos , Temperatura , Escherichia coli/genética , Escherichia coli/metabolismo , Carbono/metabolismo
8.
PeerJ ; 11: e16596, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-38077423

RESUMO

Background: Electric eels (Electrophorus sp.) are known for their ability to produce electric organ discharge (EOD) reaching voltages of up to 860 V. Given that gene transfer via intense electrical pulses is a well-established technique in genetic engineering, we hypothesized that electric eels could potentially function as a gene transfer mechanism in their aquatic environment. Methods: To investigate this hypothesis, we immersed zebrafish larvae in water containing DNA encoding the green fluorescent protein (GFP) and exposed them to electric eel's EOD. Results and Discussion: Some embryos exhibited a mosaic expression of green fluorescence, in contrast to the control group without electrical stimulation, which showed little distinct fluorescence. This suggests that electric eel EOD has the potential to function as an electroporator for the transfer of DNA into eukaryotic cells. While electric eel EOD is primarily associated with behaviors related to sensing, predation, and defense, it may incidentally serve as a possible mechanism for gene transfer in natural environment. This investigation represents the initial exploration of the uncharted impact of electric eel EOD, but it does not directly establish its significance within the natural environment. Further research is required to understand the ecological implications of this phenomenon.


Assuntos
Órgão Elétrico , Peixe-Zebra , Animais , Órgão Elétrico/fisiologia , Electrophorus/fisiologia , Peixe-Zebra/genética , DNA , Comportamento Predatório/fisiologia
9.
Adv Ther ; 40(9): 4074-4092, 2023 09.
Artigo em Inglês | MEDLINE | ID: mdl-37452961

RESUMO

INTRODUCTION: This multicenter, randomized, comparative, and investigator-masked crossover clinical trial sought to compare the efficacy and tolerability of fixed combinations of 0.1% brimonidine/0.5% timolol (BTFC) versus 1% dorzolamide/0.5% timolol (DTFC) as adjunctive therapies to prostaglandin analogues. METHODS: A total of 110 patients with open-angle glaucoma or ocular hypertension previously treated with prostaglandin analogue monotherapy were randomized to receive either BTFC or DTFC as adjunctive therapy for 8 weeks. These patients were then crossed over to the alternative treatment arm for another 8 weeks. The reduction in intraocular pressure (IOP) (primary outcome), occurrence of adverse events, ocular discomfort after instillation, and patient preference (secondary outcomes) were recorded through patient interviews. RESULTS: BTFC instillation for 8 weeks reduced IOP by 3.55 mmHg, demonstrating non-inferiority to DTFC instillation (3.60 mmHg; P < 0.0001, mixed-effects model). Although adverse events were rare with both combinations, patients reported greater discomfort with DTFC than with BTFC (P < 0.0001). More patients preferred BTFC (P < 0.0001) over DTFC, as BTFC caused minimal or no eye irritation. CONCLUSION: As BTFC offered better tolerability than DTFC with comparable reduction in IOP, we recommend it as an alternative for patients who experience ocular discomfort with DTFC-prostaglandin analogue combination therapy. TRIAL REGISTRATION NUMBER: jRCTs051190125.


Patients with glaucoma who require further reduction in intraocular pressure while undergoing monotherapy with prostaglandin analogue ophthalmic solution have been prescribed two enhanced treatment options: 0.1% brimonidine/0.5% timolol fixed combination ophthalmic solution (BTFC) and 1% dorzolamide/0.5% timolol fixed combination ophthalmic solution (DTFC). The Aibeta Crossover Study Group in Japan compared the efficacy and tolerability of fixed combinations of BTFC versus DTFC when an additional fixed combination ophthalmic solution was prescribed in patients with open-angle glaucoma or ocular hypertension who had been treated with prostaglandin analogue monotherapy. We recruited 110 patients previously treated with prostaglandin analogue monotherapy at 20 clinical centers in Japan, then randomly assigned them to two alternative treatment groups: the BTFC to DTFC group or the DTFC to BTFC group, as an adjunctive therapy to prostaglandin analogues for total of 16 weeks. We compared the reduction in intraocular pressure, occurrence of side effects, eye discomfort after instillation, and patient preference between BTFC versus DTFC instillations. The intraocular pressure reduction of BTFC instillation was comparable to that of DTFC instillation, showing non-inferiority to DTFC (3.55 mmHg vs. 3.60 mmHg; P < 0.0001, mixed-effects model). Both eye drops caused few side effects; however, patients felt greater eye discomfort with DTFC than with BTFC (P < 0.0001). Because of less eye irritation, more patients preferred BTFC (P < 0.0001) over DTFC. We can recommend using BTFC for patients who feel eye discomfort with DTFC­prostaglandin analogue combination therapy.


Assuntos
Glaucoma de Ângulo Aberto , Timolol , Humanos , Timolol/efeitos adversos , Glaucoma de Ângulo Aberto/tratamento farmacológico , Estudos Cross-Over , Anti-Hipertensivos/efeitos adversos , Soluções Oftálmicas/uso terapêutico , Tartarato de Brimonidina/uso terapêutico , Pressão Intraocular , Prostaglandinas Sintéticas/uso terapêutico , Combinação de Medicamentos
10.
ACS Appl Mater Interfaces ; 15(19): 23299-23305, 2023 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-37140359

RESUMO

A copper-zirconia composite having an evenly distributed lamellar texture, Cu#ZrO2, was synthesized by promoting nanophase separation of the Cu51Zr14 alloy precursor in a mixture of carbon monoxide (CO) and oxygen (O2). High-resolution electron microscopy revealed that the material consists of interchangeable Cu and t-ZrO2 phases with an average thickness of 5 nm. Cu#ZrO2 exhibited enhanced selectivity toward the generation of formic acid (HCOOH) by electrochemical reduction of carbon dioxide (CO2) in aqueous media at a Faradaic efficiency of 83.5% at -0.9 V versus the reversible hydrogen electrode. In situ Raman spectroscopy has revealed that a bifunctional interplay between the Zr4+ sites and the Cu boundary leads to amended reaction selectivity along with a large number of catalytic sites.

11.
Front Bioeng Biotechnol ; 11: 1114946, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36896015

RESUMO

Polyhydroxyalkanoate (PHA) synthases (PhaCs) are key enzymes in PHA polymerization. PhaCs with broad substrate specificity are attractive for synthesizing structurally diverse PHAs. In the PHA family, 3-hydroxybutyrate (3HB)-based copolymers are industrially produced using Class I PhaCs and can be used as practical biodegradable thermoplastics. However, Class I PhaCs with broad substrate specificities are scarce, prompting our search for novel PhaCs. In this study, four new PhaCs from the bacteria Ferrimonas marina, Plesiomonas shigelloides, Shewanella pealeana, and Vibrio metschnikovii were selected via a homology search against the GenBank database, using the amino acid sequence of Aeromonas caviae PHA synthase (PhaCAc), a Class I enzyme with a wide range of substrate specificities, as a template. The four PhaCs were characterized in terms of their polymerization ability and substrate specificity, using Escherichia coli as a host for PHA production. All the new PhaCs were able to synthesize P(3HB) in E. coli with a high molecular weight, surpassing PhaCAc. The substrate specificity of PhaCs was evaluated by synthesizing 3HB-based copolymers with 3-hydroxyhexanoate, 3-hydroxy-4-methylvalerate, 3-hydroxy-2-methylbutyrate, and 3-hydroxypivalate monomers. Interestingly, PhaC from P. shigelloides (PhaCPs) exhibited relatively broad substrate specificity. PhaCPs was further engineered through site-directed mutagenesis, and the variant resulted in an enzyme with improved polymerization ability and substrate specificity.

12.
Angew Chem Int Ed Engl ; 62(17): e202300640, 2023 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-36914572

RESUMO

An unexplored tin oxide crystal phase (Sn3 O4 ) was experimentally synthesized via a facile hydrothermal method. After tuning the often-neglected parameters for the hydrothermal synthesis, namely the degree of filling of the precursor solution and the gas composition in the reactor head space, an unreported X-ray diffraction pattern was discovered. Through various characterization studies, such as Rietveld analysis, energy dispersive X-ray spectroscopy, and first-principles calculations, this novel material was characterized as orthorhombic mixed-valence tin oxide with the composition SnII 2 SnIV O4 . This orthorhombic tin oxide is a new polymorph of Sn3 O4 , which differs from the reported conventional monoclinic structure. Computational and experimental analyses showed that orthorhombic Sn3 O4 has a smaller band gap (2.0 eV), enabling greater absorption of visible light. This study is expected to improve the accuracy of hydrothermal synthesis and aid the discovery of new oxide materials.

13.
Phys Chem Chem Phys ; 25(1): 255-261, 2022 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-36477553

RESUMO

The trade-off relationship between narrowing the bandgap and achieving sufficient redox potentials accounts for the hindrance to the development of an efficient photocatalyst. Most of the previous researchers attempt to narrow the bandgap of semiconductors by impurity doping to achieve visible-light sensitivity, but this approach causes the losses of their oxidation and/or reduction ability. Conversely, this study presents a bandgap widening strategy by doping to improve the redox potential of photogenerated carriers. Employing first-principles simulations, we propose the lanthanum-doped bismuth vanadate (La-BiVO4) photocatalyst as a wider-bandgap semiconductor exhibiting stronger oxidation ability compared to pristine BiVO4, and the results revealed that the bismuth orbital in the valence band (VB) was diluted by lanthanum-ion doping, while the VB shifted to a higher potential (positively shifted). Thereafter, a La-BiVO4 powder was synthesized via a solid-state reaction, after which its activity was evaluated in the photocatalytic oxidation of 2-propanol (IPA). La-BiVO4 exhibited bandgap widening; thus, the number of absorbed photons under visible-light irradiation was lower than that of pristine BiVO4. However, the quantum efficiency (QE) of La-BiVO4 for the oxidation of IPA was higher than that of the pristine BiVO4. Consequently, the photocatalytic reaction rate of La-BiVO4 was superior to that of pristine BiVO4 under the same visible-light irradiation conditions. Although the bandgap of La-BiVO4 is widened, it is still sensitive to the cyan-light region, which is the strongest in the sunlight spectrum. These results demonstrate that the orbital dilution strategy by impurity elemental doping is effective for bandgap widening and contributes to improving the oxidation and/or reduction ability of the photogenerated charge carriers. This study elucidates the possibility of boosting photocatalytic performances via bandgap widening.

14.
Sci Rep ; 12(1): 15087, 2022 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-36064732

RESUMO

Toxic puffers contain the potent neurotoxin, tetrodotoxin (TTX). Although TTX is considered to serve as a defense substance, previous behavioral studies have demonstrated that TTX acts as an attractive pheromone for some toxic puffers. To elucidate the physiological mechanism of putative pheromonal action of TTX, we examined whether grass puffers Takifugu alboplumbeus can detect TTX. Electroolfactogram (EOG) results suggest that the olfactory epithelium (OE) of grass puffers responded to a type of TTX analog (5,6,11-trideoxyTTX), although it did not respond to TTX. We also examined the attractive action of 5,6,11-trideoxyTTX on grass puffers by recording their swimming behavior under dark conditions. Grass puffers preferred to stay on the side of the aquarium where 5,6,11-trideoxyTTX was administered, and their swimming speed decreased. Additionally, odorant-induced labeling of olfactory sensory neurons by immunohistochemistry against neural activity marker (phosphorylated extracellular signal regulated kinase; pERK) revealed that labeled olfactory sensory neurons were localized in the region surrounding "islets" where there was considered as nonsensory epithelium. 5,6,11-trideoxyTTX has been known to accumulate in grass puffers, but its toxicity is much lower (almost nontoxic) than TTX. Our results suggest that toxic puffers may positively use this TTX analog, which has been present in their body with TTX but whose function was unknown, as an odorant for chemical communication or effective TTX accumulation.


Assuntos
Odorantes , Takifugu , Animais , Tetrodotoxina/análogos & derivados , Tetrodotoxina/toxicidade
15.
Chem Senses ; 472022 01 01.
Artigo em Inglês | MEDLINE | ID: mdl-35580574

RESUMO

Toxic puffers accumulate their defense substance (tetrodotoxin; TTX) through the food chain. Although the previous study suggests that 5,6,11-trideoxyTTX, a nontoxic TTX analog detected simultaneously with TTX in toxic puffers or their prey, acts as an olfactory chemoattractant for grass puffers, it is unclear whether toxic puffers are commonly attracted to 5,6,11-trideoxyTTX, and which types of olfactory sensory neurons (OSNs) detect 5,6,11-trideoxyTTX. Here, we demonstrated that green spotted puffer, a phylogenetically distant species from the grass puffer, is attracted to 5,6,11-trideoxyTTX. 5,6,11-TrideoxyTTX administration made green spotted puffers stay longer at the administered site, whereas a food odor (l-Arg) made them actively swim throughout the aquarium. Attractive responses were not observed when TTX or its vehicle was administered, nor when 5,6,11-trideoxyTTX was administered to anosmic fish. Furthermore, double immunohistochemistry with activity marker and crypt OSN marker antibodies labeled oval cells with apical invagination on the olfactory epithelium surface treated with 5,6,11-trideoxyTTX. These results suggest that 5,6,11-trideoxyTTX acts as an olfactory chemoattractant detected by crypt OSNs, and attraction to 5,6,11-trideoxyTTX odor appears to be a trait shared by toxic puffers for social communication or effective toxification.


Assuntos
Neurônios Receptores Olfatórios , Tetraodontiformes , Animais , Fatores Quimiotáticos , Odorantes , Mucosa Olfatória , Tetrodotoxina/química , Tetrodotoxina/farmacologia
16.
Bioengineering (Basel) ; 9(5)2022 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-35621506

RESUMO

A new polythioester (PTE), poly(3-mercapto-2-methylpropionate) [P(3M2MP)], and its copolymer with 3-hydroxybutyrate (3HB) were successfully biosynthesized from 3-mercapto-2-methylpropionic acid as a structurally-related precursor. This is the fourth PTE of biological origin and the first to be α-methylated. P(3M2MP) was biosynthesized using an engineered Escherichia coli LSBJ, which has a high molecular weight, amorphous structure, and elastomeric properties, reaching 2600% elongation at break. P(3HB-co-3M2MP) copolymers were synthesized by expressing 3HB-supplying enzymes. The copolymers were produced with high content in the cells and showed a high 3M2MP unit incorporation of up to 77.2 wt% and 54.8 mol%, respectively. As the 3M2MP fraction in the copolymer increased, the molecular weight decreased and the polymers became softer, more flexible, and less crystalline, with lower glass transition temperatures and higher elongations at break. The properties of this PTE were distinct from those of previously biosynthesized PTEs, indicating that the range of material properties can be further expanded by introducing α-methylated thioester monomers.

17.
Chem Sci ; 12(34): 11306-11315, 2021 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-34667541

RESUMO

High-entropy alloys (HEAs) are near-equimolar alloys comprising five or more elements. In recent years, catalysis using HEAs has attracted considerable attention across various fields. Herein, we demonstrate the facile synthesis of nanoporous ultra-high-entropy alloys (np-UHEAs) with hierarchical porosity via dealloying. These np-UHEAs contain up to 14 elements, namely, Al, Ag, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Rh, Ru, and Ti. Furthermore, they exhibit high catalytic activities and electrochemical stabilities in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic media, superior to that of commercial Pt/graphene and IrO2 catalysts. Our results offer valuable insights for the selection of elements as catalysts for various applications.

18.
Nanoscale ; 13(45): 18987-18995, 2021 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-34522917

RESUMO

Heterointerfaces with an epitaxial relationship, self-assembled nanocomposites of Pt(111)/CeO2(111) 60°, were successfully formed by simple oxidation of Pt5Ce alloy. Oxygen dissolution into the alloy causes spacial periodic compositional perturbation by atomic segregation, specifically, by local diffusion of Pt and Ce atoms. A striped pattern of Pt and CeO2 with a 4-5 nm periodicity formed through phase transformation of the Pt-rich alloy and oxidation of the Ce-rich alloy, respectively. Notably, a fully epitaxial relationship between the Pt and CeO2 phases was observed even in the initial stage. With continued annealing, the crystals rotated into an energetically favorable orientation with respect to the remaining (111)Pt//(111)CeO2. The alloy oxidation and its resulting nanoscale phase-separation behavior were verified in an ex situ annealing experiment of an alloy specimen, which had been first thinned by a focused ion beam. Changing the oxygen partial pressure to the reaction interface may alter the orientation relationship between the hexagonal close-packed Pt5Ce structure and face-centered cubic Pt/CeO2 structure, thereby altering the growth direction of the separated phases. These findings present a pathway for the self-assembly of epitaxial Pt(111)/CeO2(111) interface and are expected to assist the structural design of metal-oxide nanocomposites.

19.
Chem Commun (Camb) ; 57(65): 8007-8010, 2021 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-34319340

RESUMO

Steam reforming of methane (SRM) requires high temperatures to be promoted, and the production of carbon dioxide from the side reaction has also become a problem. In this study, we separated the reaction sites for SRM to suppress CO2 generation using a gas-phase photoelectrochemical (GPEC) system with a cell coated with a Pt/YSZ powder catalyst on an oxygen ion-conductive YSZ pellet, where the reaction was assisted by light irradiation. As a result, SRM proceeded stoichiometrically and the production of CO2 was suppressed. We expect the findings obtained by the GPEC system will be useful in providing design guidelines for photocatalysts.

20.
J Comp Neurol ; 529(1): 87-110, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-32337719

RESUMO

The nucleus prethalamicus (PTh) receives fibers from the optic tectum and then projects to the dorsal telencephalon in the yellowfin goby Acanthogobius flavimanus. However, it remained unclear whether the PTh is a visual relay nucleus, because the optic tectum receives not only visual but also other sensory modalities. Furthermore, precise telencephalic regions receiving prethalamic input remained unknown in the goby. We therefore investigated the full set of afferent and efferent connections of the PTh by direct tracer injections into the nucleus. Injections into the PTh labeled cells in the optic tectum, ventromedial thalamic nucleus, central and medial parts of the dorsal telencephalon, and caudal lobe of the cerebellum. We found that the somata of most tecto-prethalamic neurons are present in the stratum periventriculare. Their dendrites ascend to reach the major retinorecipient layers of the tectum. The PTh is composed of two subnuclei (medial and lateral) and topographic organization was appreciated only for tectal projections to the lateral subnucleus (PTh-l), which also receives sparse retinal projections. In contrast, the medial subnucleus receives fibers only from the medial tectum. We found that the PTh projects to nine subregions in the dorsal telencephalon and four in the ventral telencephalon. Furthermore, cerebellar injections revealed that cerebello-prethalamic fibers cross the midline twice to innervate the PTh-l on both sides. The present study is the first detailed report on the full set of the connections of PTh, which suggests that the PTh relays visual information from the optic tectum to the telencephalon.


Assuntos
Vias Aferentes/anatomia & histologia , Vias Eferentes/anatomia & histologia , Colículos Superiores/anatomia & histologia , Telencéfalo/anatomia & histologia , Núcleos Talâmicos/anatomia & histologia , Vias Visuais/anatomia & histologia , Vias Aferentes/citologia , Animais , Vias Eferentes/citologia , Feminino , Peixes , Masculino , Colículos Superiores/citologia , Telencéfalo/citologia , Núcleos Talâmicos/citologia , Vias Visuais/citologia
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