Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 35
Filtrar
Mais filtros








Base de dados
Intervalo de ano de publicação
1.
Rev Sci Instrum ; 93(2): 023902, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-35232157

RESUMO

AC-calorimetry was developed for a cubic-anvil-type pressure apparatus, which can explore the electromagnetic properties of matter over temperatures of 2-300 K and pressures of 0-15 GPa. This method was designed to observe the specific heat of fragile crystals that are difficult to mold into desired forms, such as ß-Na0.33V2O5 and BaFe2S3. The calorimeter has two main components: a thermometer and a heater. We employed an AuFe (0.07 mol. %)-Chromel thermocouple and NiCr alloy foil/wire as the thermometer and heater, respectively. Using this calorimetry, we successfully observed the pressure dependencies of several transition temperatures in ß-Na0.33V2O5 and the jump in the specific heat (ΔCac/T) at the superconducting transition in Pb-metal when under pressure. Meanwhile, the pressure dependencies of the observed ΔCac/T do not coincide with the literature, which may be attributed to the pressure dependence of the thermoelectric power for the AuFe-Chromel thermocouple at around 5 K.

2.
Plant Physiol ; 186(1): 767-781, 2021 05 27.
Artigo em Inglês | MEDLINE | ID: mdl-33620479

RESUMO

The cytochrome P450 CYP78A5/KLUH in Arabidopsis thaliana is predicted to be involved in the synthesis of a mobile signal molecule that has a pleiotropic function that is distinct from classical phytohormones. CYP78A5 has five close relatives in Arabidopsis. We first investigated their functions, focusing on the plastochron, leaf size, and leaf senescence. Our analyses revealed that CYP78A5 and CYP78A7 are involved in the plastochron and leaf size, and CYP78A6 and CYP78A9 are involved in leaf senescence. Complementation analyses using heterologous promoters and expression analyses suggested that CYP78A isoforms have a common biochemical function and are functionally differentiated via organ-specific expression. The altered meristem program1 (amp1) carboxypeptidase mutant shows a phenotype very similar to that of the cyp78a5 mutant. Complementation analyses using boundary and organizing center-specific promoters suggested that both CYP78A5 and AMP1 act in a non-cell-autonomous manner. Analyses of multiple cyp78a mutants and crosses between cyp78a and amp1 mutants revealed that AMP1/LIKE AMP1 (LAMP1) and CYP78A isoforms regulate plastochron length and leaf senescence in the same genetic pathway, whereas leaf size is independently regulated. Furthermore, we detected feedback regulation between CYP78A6/CYP78A9 and AMP1 at the gene expression level. These observations raise the possibility that AMP1 and CYP78A isoforms are involved in the synthesis of the same mobile signal molecule, and suggest that AMP1 and CYP78A signaling pathways have a very close, albeit complex, functional relationship.


Assuntos
Proteínas de Arabidopsis/genética , Arabidopsis/genética , Regulação da Expressão Gênica , Pleiotropia Genética , Arabidopsis/metabolismo , Proteínas de Arabidopsis/metabolismo
3.
Breed Sci ; 70(3): 331-341, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32714055

RESUMO

Cadmium (Cd) is as an extremely toxic metal that can contaminate agricultural soils. To reduce the risk of Cd intake in food cereals, the development of cultivars with low grain Cd concentration (GCC) is an effective countermeasure. We analyzed quantitative trait loci (QTLs) for GCC in a doubled haploid (DH) common wheat (Triticum aestivum L.) population derived from 'Chugoku 165' (low GCC) × 'Chukei 10-22' (high GCC). We found novel loci for low GCC on the short arm of chromosome 4B and on the long arm of chromosome 6B. These QTLs accounted for 9.4%-25.4% (4B) and 9.0%-17.8% (6B) of the phenotypic variance in the DH population. An association analysis with 43 cultivars identified 3 loci at these QTLs: QCdc.4B-kita, QCdc.6B-kita1, and QCdc.6B-kita2. In contrast to durum wheat and barley, no QTL was detected on the chromosomes of homeologous group 5 for heavy metal P1B-type ATPase 3. These results will contribute to marker-assisted selection for low GCC in breeding of common wheat.

4.
Front Plant Sci ; 11: 564, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32508856

RESUMO

Leaf senescence is induced by various internal and external stimuli. Dark-induced senescence has been extensively investigated, but the detailed mechanism underlying it is not well understood. The red light/far-red light receptor phytochrome B and its downstream transcription factors, PYHTOCHROME INTERACTING FACTORs (PIFs) 4 and 5, are known to play an important role in dark-induced senescence. Furthermore, the senescence-inducing phytohormones, ethylene and abscisic acid (ABA) are reported to be involved in dark-induced senescence. In this study, we analyzed the relationship between ethylene, ABA and PIFs in dark-induced leaf senescence. A triple mutant of the core ABA signaling components; SNF1-related protein kinases 2D (SRK2D), SRK2E, and SRK2I, displayed an ABA insensitive phenotype in ABA-induced senescence, whilst the ethylene insensitive mutant ein2 demonstrated low sensitivity to ABA, suggesting that ethylene signaling is involved in ABA-induced senescence. However, the pif4 pif5 mutant did not display low sensitivity to ABA, suggesting that PIF4 and PIF5 act upstream of ABA signaling. Although PIF4 and PIF5 reportedly regulate ethylene production, the triple mutant ein2 pif4 pif5 showed a stronger delayed senescence phenotype than ein2 or pif4 pif5, suggesting that EIN2 and PIF4/PIF5 partially regulate leaf senescence independently of each other. While direct target genes for PIF4 and PIF5, such as LONG HYPOCOTYL IN FAR-RED1 (HFR1) and PHYTOCHROME INTERACTING FACTOR 3-LIKE 1 (PIL1), showed transient upregulation under dark conditions (as is seen in the shade avoidance response), expression of STAY GREEN1 (SGR1), ORESARA1 (ORE1) and other direct target genes of PIF5, continued to increase during dark incubation. It is possible that transcription factors other than PIF4 and PIF5 are involved in the upregulation of SGR1 and ORE1 at a later stage of dark-induced senescence. Possible candidates are senescence-induced senescence regulators (SIRs), which include the NAC transcription factors ORE1 and AtNAP. In fact, ORE1 is known to bind to the SGR1 promoter and promotes its expression. It is therefore inferred that the phytochrome-PIF pathway regulates initial activation of senescence and subsequently, induced SIRs reinforce leaf senescence during dark-induced senescence.

5.
J Chem Phys ; 153(6): 064702, 2020 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-35287437

RESUMO

We have investigated the adsorption and thermal reaction processes of NO with silicene spontaneously formed on the ZrB2/Si(111) substrate using synchrotron radiation x-ray photoelectron spectroscopy (XPS) and density-functional theory calculations. NO is dissociatively adsorbed on the silicene surface at 300 K. An atomic nitrogen is bonded to three Si atoms most probably by a substitutional adsorption with a Si atom of silicene (N≡Si3). An atomic oxygen is inserted between two Si atoms of the silicene (Si-O-Si). With increasing NO exposure, the two-dimensional honeycomb silicene structure gets destroyed, judging from the decay of typical Si 2p spectra for silicene. After a large amount of NO exposure, the oxidation state of Si becomes Si4+ predominantly, and the intensity of the XPS peaks of the ZrB2 substrate decreases, indicating that complicated silicon oxinitride species have developed three-dimensionally. By heating above 900 K, the oxide species start to desorb from the surface, but nitrogen-bonded species still exist. After flashing at 1053 K, no oxygen species is observed on the surface; SiN species are temporally formed as a metastable species and BN species also start to develop. In addition, the silicene structure is restored on the ZrB2/Si(111) substrate. After prolonged heating at 1053 K, most of nitrogen atoms are bonded to B atoms to form a BN layer at the topmost surface. Thus, BN-covered silicene is formed on the ZrB2/Si(111) substrate by the adsorption of NO at 300 K and prolonged heating at 1053 K.

6.
Plant Biotechnol (Tokyo) ; 36(1): 39-42, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31275047

RESUMO

Several selection markers for the screening of transformants have been developed; however, simple and reliable methods are generally preferred. We have developed a novel visible selection system for the identification of transformants in Arabidopsis thaliana that does not require any special reagent and/or equipment except using the albino-cotyledon mutant cyo1. In this system, the pCYO vector carrying the CYO1 genomic fragment as a selection marker is introduced into the cyo1 mutant. Transformation is performed by the Agrobacterium-mediated floral dip method and resultant T1 seeds are sown in soil. Seedlings with green cotyledons, not albino, are expected to be 'complemented' transformants with the transgene of interest. This system provides a very simple selection method that can be performed without any special equipment, reagent, sterile conditions, or UV illumination. We have constructed three vectors, (1) pCYO1, an empty vector; (2) pCYO2, an overexpression vector carrying CaMV35S promoter; and (3) pCYO3, a vector for genome editing, carrying the CRISPR/Cas9 cassette. Example transformation experiments using these vectors, including genome editing, are shown.

7.
Inorg Chem ; 58(21): 14304-14315, 2019 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-30964663

RESUMO

Anomalous successive structural transitions in layered 1T-CrSe2 with an unusual Cr4+ valency were investigated by synchrotron X-ray diffraction. 1T-CrSe2 exhibits dramatic structural changes in in-plane Cr-Cr and interlayer Se-Se distances, which originate from two interactions: (i) in-plane Cr-Cr interactions derived from Peierls-like trimerization instabilities on the orbitally assisted one-dimensional chains and (ii) interlayer Se-Se interactions through p-p hybridization. As a result, 1T-CrSe2 has the unexpected ground state of an antiferromagnetic metal with multiple Cr linear trimers with three-center-two-electron σ bonds. Interestingly, partial substitution of Se for S atoms in 1T-CrSe2 changes the ground state from an antiferromagnetic metal to an insulator without long-range magnetic ordering, which is due to the weakening of interlayer interactions between anions. The unique low-temperature structures and electronic states of this system are determined by the competition and cooperation of in-plane Cr-Cr and interlayer Se-Se interactions.

8.
J Hum Genet ; 63(6): 755-759, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29556035

RESUMO

Pathogenic variants in specific complement-related genes lead to atypical hemolytic uremic syndrome (aHUS). Some reports have indicated that patients with digenic variants in these genes might present severer phenotypes. Upon detecting novel intronic variants, transcriptional analysis is necessary to prove pathogenicity; however, when intronic variants are located in intron 1 and, as a result, no transcript is produced, no appropriate method had been established to reveal the pathogenicity. Recently, the minigene assay was used to assess the pathogenicity of intronic variants. Here, we report an infantile case of aHUS caused by digenic mutations in two different complement-related genes, C3 and MCP. Targeted sequencing detected a known variant in C3 and a novel variant in the intron 1 splicing donor site of MCP. To assess the pathogenicity of this intronic variant, we conducted functional splicing assay using a minigene construct and quantitative PCR analysis of the MCP transcript, revealing the pathogenicity of the intronic variant. In conclusion, the minigene assay revealed the pathogenicity of the intron 1 splicing donor site variant for the first time. This case showed a severe phenotype of infantile-onset aHUS associated with digenic variants in two complement-related genes.


Assuntos
Complemento C3/genética , Síndrome Hemolítico-Urêmica/genética , Proteína Cofatora de Membrana/genética , Mutação , Splicing de RNA , Idade de Início , Humanos , Lactente , Íntrons , Masculino , Fenótipo , Reação em Cadeia da Polimerase , RNA Mensageiro/genética
9.
Chemistry ; 23(63): 15879-15883, 2017 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-28994203

RESUMO

The physical properties of novel cluster-based triangular lattice antiferromagnets Na3 A2 (MoO4 )2 Mo3 O8 (A=In, Sc), synthesized through a topochemical Na-intercalation to nonmagnetic Na2 A2 (MoO4 )2 Mo3 O8 , are reported. The S=1/2 [Mo3 ]11+ clusters form a regular triangular lattice, which gives the magnetic system a strong geometrical spin frustration effect. Despite the strong antiferromagnetic couplings among [Mo3 ]11+ clusters, they show no long-range magnetic orderings down to 0.5 K with the finite residual magnetic entropy. The ground states of Na3 A2 (MoO4 )2 Mo3 O8 have been characterized as a quantum spin liquid, owing to the strong spin frustration of cluster spins on the triangular lattice.

10.
Nat Commun ; 8(1): 638, 2017 09 21.
Artigo em Inglês | MEDLINE | ID: mdl-28935962

RESUMO

Ultrafast control of magnets using femtosecond light pulses attracts interest regarding applications and fundamental physics of magnetism. Antiferromagnets are promising materials with magnon frequencies extending into the terahertz range. Visible or near-infrared light interacts mainly with the electronic orbital angular momentum. In many magnets, however, in particular with iron-group ions, the orbital momentum is almost quenched by the crystal field. Thus, the interaction of magnons with light is hampered, because it is only mediated by weak unquenching of the orbital momentum by spin-orbit interactions. Here we report all-optical excitation of magnons with frequencies up to 9 THz in antiferromagnetic CoO with an unquenched orbital momentum. In CoO, magnon modes are coupled oscillations of spin and orbital momenta with comparable amplitudes. We demonstrate excitations of magnon modes by directly coupling light with electronic orbital angular momentum, providing possibilities to develop magneto-optical devices operating at several terahertz with high output-to-input ratio.Light pulses can control magnetism in a material, and the effective creation of magnetic oscillations leads to spintronic devices with higher efficiency. Here, the authors increase the efficiency of magnon excitation by using a material in which orbital angular momenta are not quenched.

11.
Inorg Chem ; 56(6): 3483-3488, 2017 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-28240540

RESUMO

We grew large single crystals of the cluster magnet Nb3Cl8 with a magnetic triangular lattice and investigated its magnetic properties and crystal structure. In Nb3Cl8, the [Nb3]8+ cluster has a single unpaired spin, making it an S = 1/2 triangular lattice anti-ferromagnet. At low temperatures, Nb3Cl8 exhibits a magnetic-nonmagnetic phase transition driven by a charge disproportionation, in which the paramagnetic [Nb3]8+ clusters transform into alternating layers of nonmagnetic [Nb3]7+ and [Nb3]9+ clusters. The observed exotic phenomenon with the strong correlation between the magnetism and structure are based on the nature of the cluster magnetism.

12.
J Phys Condens Matter ; 28(35): 355602, 2016 09 07.
Artigo em Inglês | MEDLINE | ID: mdl-27385539

RESUMO

We synthesized polycrystalline samples of the fluorine-substituted pyrochlore rhenates Cd2Re2O7-x F x , and investigated their magnetic, transport and structural properties. The transition temperature T s1, where each Re4 tetrahedron in the Re pyrochlore network alternately expands and contracts, decreases with increasing x from 200 K at x = 0 to 100 K at x = 0.5. The strong x dependence of the magnetic and transport properties at the low-temperature phase indicates that the driving force of structural phase transition is fluctuations of the tetramer spin singlet formation in order to release the spin frustration in the pyrochlore lattice. Furthermore, we found unconventional superconducting properties in Cd2Re2O7-x F x . It was found that the superconducting phase transition temperature T c markedly decreases with increasing x, suggesting that the addition of imperfection suppresses a condensation of Cooper-pair. In addition, the estimated upper critical field at zero temperature exceeds the Pauli paramagnetic limit and increases with increasing x in spite of the reduction of T c. Hence, Cd2Re2O7-x F x is suggested to be an exotic superconductor realized in the itinerant electron systems on a spin frustrated lattice.

13.
Inorg Chem ; 55(15): 7407-13, 2016 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-27400024

RESUMO

Physical properties of new S = 3/2 triangular-lattice compounds LiCrSe2, LiCrTe2, and NaCrTe2 have been investigated by X-ray diffraction and magnetic measurements. These compounds crystallize in the ordered NiAs-type structure, where alkali metal ions and Cr atoms stack alternately. Despite their isomorphic structures, magnetic properties of these three compounds are different; NaCrTe2 has an A-type spin structure with ferromagnetic layers, LiCrTe2 is likely to exhibit a helical spin structure, and LiCrSe2 shows a first-order-like phase transition from the paramagnetic trigonal phase to the antiferromagnetic monoclinic phase. In these compounds and the other chromium chalcogenides with a triangular lattice, we found a general relationship between the Curie-Weiss temperature and magnetic structures. This relation indicates that the competition between the antiferromagnetic direct d-d exchange interaction and the ferromagnetic superexchange interaction plays an important role in determining the ground state of chromium chalcogenides.

14.
Nat Commun ; 6: 8854, 2015 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-26564801

RESUMO

Recent research indicates that the cooling trend in the tropical Pacific Ocean over the past 15 years underlies the contemporaneous hiatus in global mean temperature increase. During the hiatus, the tropical Pacific Ocean displays a La Niña-like cooling pattern while sea surface temperature (SST) in the Indian Ocean has continued to increase. This SST pattern differs from the well-known La Niña-induced basin-wide cooling across the Indian Ocean on the interannual timescale. Here, based on model experiments, we show that the SST pattern during the hiatus explains pronounced regional anomalies of rainfall in the Asian monsoon region and thermodynamic effects due to specific humidity change are secondary. Specifically, Indo-Pacific SST anomalies cause convection to intensify over the tropical western Pacific, which in turn suppresses rainfall in mid-latitude East Asia through atmospheric teleconnection. Overall, the tropical Pacific SST effect opposes and is greater than the Indian Ocean SST effect.

15.
Proc Natl Acad Sci U S A ; 112(37): 11519-23, 2015 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-26324917

RESUMO

Since the discovery of spin glasses in dilute magnetic systems, their study has been largely focused on understanding randomness and defects as the driving mechanism. The same paradigm has also been applied to explain glassy states found in dense frustrated systems. Recently, however, it has been theoretically suggested that different mechanisms, such as quantum fluctuations and topological features, may induce glassy states in defect-free spin systems, far from the conventional dilute limit. Here we report experimental evidence for existence of a glassy state, which we call a spin jam, in the vicinity of the clean limit of a frustrated magnet, which is insensitive to a low concentration of defects. We have studied the effect of impurities on SrCr9pGa12-9pO19 [SCGO(p)], a highly frustrated magnet, in which the magnetic Cr(3+) (s = 3/2) ions form a quasi-2D triangular system of bipyramids. Our experimental data show that as the nonmagnetic Ga(3+) impurity concentration is changed, there are two distinct phases of glassiness: an exotic glassy state, which we call a spin jam, for the high magnetic concentration region (p > 0.8) and a cluster spin glass for lower magnetic concentration (p < 0.8). This observation indicates that a spin jam is a unique vantage point from which the class of glassy states of dense frustrated magnets can be understood.

16.
Plant Physiol ; 169(1): 138-47, 2015 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-25979917

RESUMO

Leaf senescence is not a passive degenerative process; it represents a process of nutrient relocation, in which materials are salvaged for growth at a later stage or to produce the next generation. Leaf senescence is regulated by various factors, such as darkness, stress, aging, and phytohormones. Strigolactone is a recently identified phytohormone, and it has multiple functions in plant development, including repression of branching. Although strigolactone is implicated in the regulation of leaf senescence, little is known about its molecular mechanism of action. In this study, strigolactone biosynthesis mutant strains of Arabidopsis (Arabidopsis thaliana) showed a delayed senescence phenotype during dark incubation. The strigolactone biosynthesis genes MORE AXIALLY GROWTH3 (MAX3) and MAX4 were drastically induced during dark incubation and treatment with the senescence-promoting phytohormone ethylene, suggesting that strigolactone is synthesized in the leaf during leaf senescence. This hypothesis was confirmed by a grafting experiment using max4 as the stock and Columbia-0 as the scion, in which the leaves from the Columbia-0 scion senesced earlier than max4 stock leaves. Dark incubation induced the synthesis of ethylene independent of strigolactone. Strigolactone biosynthesis mutants showed a delayed senescence phenotype during ethylene treatment in the light. Furthermore, leaf senescence was strongly accelerated by the application of strigolactone in the presence of ethylene and not by strigolactone alone. These observations suggest that strigolactone promotes leaf senescence by enhancing the action of ethylene. Thus, dark-induced senescence is regulated by a two-step mechanism: induction of ethylene synthesis and consequent induction of strigolactone synthesis in the leaf.


Assuntos
Arabidopsis/efeitos dos fármacos , Etilenos/metabolismo , Regulação da Expressão Gênica de Plantas/efeitos dos fármacos , Lactonas/farmacologia , Reguladores de Crescimento de Plantas/metabolismo , Arabidopsis/genética , Arabidopsis/fisiologia , Arabidopsis/efeitos da radiação , Proteínas de Arabidopsis/genética , Proteínas de Arabidopsis/metabolismo , Senescência Celular/efeitos dos fármacos , Escuridão , Dioxigenases/genética , Dioxigenases/metabolismo , Etilenos/farmacologia , Luz , Oxigenases/genética , Oxigenases/metabolismo , Reguladores de Crescimento de Plantas/farmacologia , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/genética , Folhas de Planta/fisiologia , Folhas de Planta/efeitos da radiação
17.
Plant Cell Physiol ; 55(10): 1763-71, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-25108243

RESUMO

The recent whole-genome sequencing of soybean (Glycine max) revealed that soybean experienced whole-genome duplications 59 million and 13 million years ago, and it has an octoploid-like genome in spite of its diploid nature. We analyzed a natural green-cotyledon mutant line, Tenshin-daiseitou. The physiological analysis revealed that Tenshin-daiseitou shows a non-functional stay-green phenotype in senescent leaves, which is similar to that of the mutant of Mendel's green-cotyledon gene I, the ortholog of SGR in pea. The identification of gene mutations and genetic segregation analysis suggested that defects in GmSGR1 and GmSGR2 were responsible for the green-cotyledon/stay-green phenotype of Tenshin-daiseitou, which was confirmed by RNA interference (RNAi) transgenic soybean experiments using GmSGR genes. The characterized green-cotyledon double mutant d1d2 was found to have the same mutations, suggesting that GmSGR1 and GmSGR2 are D1 and D2. Among the examined d1d2 strains, the d1d2 strain K144a showed a lower Chl a/b ratio in mature seeds than other strains but not in senescent leaves, suggesting a seed-specific genetic factor of the Chl composition in K144a. Analysis of the soybean genome sequence revealed four genomic regions with microsynteny to the Arabidopsis SGR1 region, which included the GmSGR1 and GmSGR2 regions. The other two regions contained GmSGR3a/GmSGR3b and GmSGR4, respectively, which might be pseudogenes or genes with a function that is unrelated to Chl degradation during seed maturation and leaf senescence. These GmSGR genes were thought to be produced by the two whole-genome duplications, and they provide a good example of such whole-genome duplication events in the evolution of the soybean genome.


Assuntos
Cotilédone/fisiologia , Duplicação Gênica , Genoma de Planta , Glycine max/genética , Mutação , Evolução Biológica
18.
Sci Rep ; 3: 2013, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23774736

RESUMO

The mid-Piacenzian climate represents the most geologically recent interval of long-term average warmth relative to the last million years, and shares similarities with the climate projected for the end of the 21(st) century. As such, it represents a natural experiment from which we can gain insight into potential climate change impacts, enabling more informed policy decisions for mitigation and adaptation. Here, we present the first systematic comparison of Pliocene sea surface temperature (SST) between an ensemble of eight climate model simulations produced as part of PlioMIP (Pliocene Model Intercomparison Project) with the PRISM (Pliocene Research, Interpretation and Synoptic Mapping) Project mean annual SST field. Our results highlight key regional and dynamic situations where there is discord between the palaeoenvironmental reconstruction and the climate model simulations. These differences have led to improved strategies for both experimental design and temporal refinement of the palaeoenvironmental reconstruction.

19.
ACS Appl Mater Interfaces ; 4(8): 4338-47, 2012 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-22850398

RESUMO

We investigated emulsions stabilized with particles of layered hexaniobate, known as a semiconductor photocatalyst, and photocatalytic degradation of dyes in the emulsions. Hydrophobicity of the niobate particles was adjusted with the intercalation of alkylammonium ions into the interlayer spaces to enable emulsification in a toluene-water system. After the modification of interlayer space with hexylammonium ions, the niobate stabilized water-in-oil (w/o) emulsions in a broad composition range. Optical microscopy showed that the niobate particles covered the surfaces of emulsion droplets and played a role of emulsifying agents. The niobate particles also enabled the generation of oil-in-water (o/w) emulsions in a limited composition range. Modification with dodecylammonium ions, which turned the niobate particles more hydrophobic, only gave w/o emulsions, and the particles were located not only at the toluene-water interface but also inside the toluene continuous phase. On the other hand, interlayer modification with butylammonium ions led to the formation of o/w emulsions. When porphyrin dyes were added to the system, the cationic dye was adsorbed on niobate particles at the emulsion droplets whereas the lipophilic dye was dissolved in toluene. Upon UV irradiation, both of the dyes were degraded photocatalytically. When the cationic and lipophilic porphyrin molecules were simultaneously added to the emulsions, both of the dyes were photodecomposed nonselectively.


Assuntos
Corantes/química , Nióbio/química , Compostos Orgânicos/química , Óxidos/química , Fotoquímica/métodos , Potássio/química , Adsorção , Catálise , Cátions , Emulsões , Íons , Microscopia/métodos , Microscopia de Fluorescência/métodos , Conformação Molecular , Óleos , Porfirinas/química , Compostos de Amônio Quaternário/química , Raios Ultravioleta , Água/química
20.
J Am Chem Soc ; 134(20): 8412-5, 2012 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-22568570

RESUMO

Dendrimer-based electron rectifiers were applied to photoconducting devices. A remarkable enhancement of the photocurrent response was observed when a zinc porphyrin as the photosensitizer was embedded in the dendritic phenylazomethine (DPA) architecture. The dendrimer-based sensitizer exhibited a 20-fold higher current response than the non-dendritic zinc porphyrin. In sharp contrast, a similar application of the dendrimer with poly(vinylcarbazole) as the electron donor resulted in a decreased response. This is consistent with the idea that the DPA facilitates electron transfer from the core to its periphery along a potential gradient, as predicted by density functional theory calculations.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA