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1.
ACS Nano ; 2020 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-32356968

RESUMO

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) have attracted intensive interest due to the direct-band-gap transition in the monolayer form, positioning them as potential next-generation materials for optoelectronic or photonic devices. However, the band-nested suppression of the recombination efficiency at higher excitation energies limits the ability to locally control and manipulate the photoluminescence of WS2 for multifunctional applications. In this work, we exploit an energy transfer method to modulate the fluorescence properties of TMDs under a larger excitation range spanning from UV to visible light. Self-assembled lanthanide (Ln)/TMD hybrids have been designed based on a low-cost and highly efficient solution-processed approach. The emission energy from Ln3+ sources can be effectively transferred to the TMD monolayers under low power exposure (0.13 mW) at room temperature, activating the characteristic monolayer fluorescence in place of Ln3+ emission signatures. The Ln/TMDs photonics can potentially tune the excitation of TMDs to provide variable yet controllable emissions. This provides a solution to the suppression of direct exciton recombination in monolayer TMDs at the band nesting resonant energy region. Our work on such Ln/TMD systems would overcome the limited excitation energy range in TMDs and extend their functionalities for optoelectronic or photonic applications.

2.
Langmuir ; 2020 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-32283939

RESUMO

Plasmon coupling-induced intense local electrical field in the gap of closely packed metal nanoparticles (NPs) has been known capable of significantly enhancing optical properties of chromophores. Here, we have investigated aggregation-induced plasmon coupling-enhanced one-photon excitation (1PE) and two-photon excitation (2PE) fluorescence of dyes using Ag NPs of three different sizes (20, 36, and 48 nm). The fluorescence of a model dye, Rhodamine B isothiocyanate (RiTC), was prequenched by attaching to Ag NPs and subsequently enhanced upon forming aggregates of Ag NPs. It was found that aggregates of larger sized Ag NPs gave larger 1PE and 2PE fluorescence enhancement on the basis of free dyes, while aggregates of smaller counterparts displayed larger enhancement on the basis of the corresponding prequenched ones. 1PE and 2PE fluorescence were enhanced by 2.5- and 10.2-fold by aggregated 48 nm Ag NPs compared to free dyes and by 8.0- and 22.5-fold by aggregated 20 nm Ag NPs compared to the quenched ones, respectively. This scheme achieved fluorescence enhancement significantly beyond the level of fluorescence recovery, much larger than conventional turn-on fluorescence probes, which is attractive for developing sensitive fluorescence turn-on-based detection with reduced background.

3.
Artigo em Inglês | MEDLINE | ID: mdl-32003098

RESUMO

Ligand-induced surface restructuring with heteroatomic doping is used to precisely modify the surface of a prototypical [Au25 (SR1 )18 ]- cluster (1) while maintaining its icosahedral Au13 core for the synthesis of a new bimetallic [Au19 Cd3 (SR2 )18 ]- cluster (2). Single-crystal X-ray diffraction studies reveal that six bidentate Au2 (SR1 )3 motifs (L2) attached to the Au13 core of 1 were replaced by three quadridentate Au2 Cd(SR2 )6 motifs (L4) to create a bimetallic cluster 2. Experimental and theoretical results demonstrate a stronger electronic interaction between the surface motifs (Au2 Cd(SR2 )6 ) and the Au13 core, attributed to a more compact cluster structure and a larger energy gap of 2 compared to that of 1. These factors dramatically enhance the photoluminescence quantum efficiency and lifetime of crystal of the cluster 2. This work provides a new route for the design of a wide range of bimetallic/alloy metal nanoclusters with superior optoelectronic properties and functionality.

4.
Angew Chem Int Ed Engl ; 59(2): 833-838, 2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31573739

RESUMO

Interpenetration in metal-organic frameworks (MOFs) is an intriguing phenomenon with significant impacts on their properties, and functional applications. Herein, we show that a 7-fold interpenetrated MOF (1) is transformed into an 8-fold interpenetrated MOF by the loss of DMF in a single-crystal-to-single-crystal manner. This is accompanied by a giant enhancement of the second harmonic generation (SHG ca. 125 times) and two-photon photoluminescence (ca. 14 times). The strengthened π-π interaction between the individual diamondoid networks and intensified oscillator strength of the molecules aid the augment of dipole moments and boost the nonlinear optical conversion efficiency. Large positive and negative thermal expansions of 1 occur at 30-150 °C before the loss of DMF. These results offer an avenue to manipulate the NLO properties of MOFs using interpenetration and provide access to tunable single-crystal NLO devices.

5.
Nanoscale ; 11(41): 19551-19560, 2019 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-31578535

RESUMO

Two-photon photodynamic therapy (2P-PDT) is a novel minimal invasive cancer treatment method with advantages of deep penetration and intrinsic three-dimensionally localized activation to precisely target cancerous tissues. However, the therapeutic efficacy of 2P-PDT is limited by small two-photon absorption cross sections of conventional organic photosensitizers. In addition, traditional photosensitizers generally exhibit weak emission and lack imaging modality. In this work, conjugated polymers and gold nanorods (Au NRs) were integrated to fabricate nano-sized photosensitizers to improve the performance of molecular photosensitizers for 2P-PDT. A molecular photosensitizer, tetraphenylporphyrin, was encapsulated into the conjugated polymer PFV to form conjugated polymer nanoparticles (CPNs), which were then covalently linked to silica coated Au NRs. In these integrated nanoparticles, the two-photon optical properties of tetraphenylporphyrin were first enhanced by fluorescence resonance energy transfer from PFV, then further enhanced by Au NRs through plasmon resonance. A silica shell was utilized as the spacer between Au NRs and CPNs to optimize the enhancement effects. Through the combined enhancement effects of energy transfer and plasmon resonance, two-photon excitation fluorescence and two-photon induced singlet oxygen generation of tetraphenylporphyrin were enhanced by up to 980- and 792-fold, respectively, at a silica spacer thickness of 9 nm. The application of these nanoparticles as photosensitizers for simultaneous two-photon imaging and 2P-PDT treatment have been demonstrated on HeLa cancer cells with high brightness and significantly enhanced cancer cell killing efficiency. These nanoparticles can act as promising nano-photosensitizers for 2P-PDT with simultaneous imaging modality.

6.
J Am Chem Soc ; 141(40): 15972-15976, 2019 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-31522501

RESUMO

Hybrid organic-inorganic perovskites (HOIPs) are a new generation of high-performance materials for solar cells and light emitting diodes. Beyond these applications, ferroelectricity and spin-related properties of HOIPs are increasingly attracting interests. The presence of strong spin-orbit coupling, allied with symmetry breaking ensured by remanent polarization, should give rise to Rashba-type splitting of electronic bands in HOIP. However, the report of both ferroelectricity and Rashba effect in HOIP is rare. Here we report the observation of robust ferroelectricity and Rashba effect in two-dimensional Dion-Jacobson perovskites.

7.
Light Sci Appl ; 8: 58, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31263557
8.
Nano Lett ; 19(8): 5109-5117, 2019 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-31248259

RESUMO

Ultrathin ferroelectrics hold great promise for modern miniaturized sensors, memories, and optoelectronic devices. However, in most ferroelectric materials, polarization is destabilized in ultrathin films by the intrinsic depolarization field. Here we report robust in-plane ferroelectricity in few-layer tin sulfide (SnS) 2D crystals that is coupled anisotropically to lattice strain. Specifically, the intrinsic polarization of SnS manifests as nanoripples along the armchair direction due to a converse piezoelectric effect. Most interestingly, such nanoripples show an odd-and-even effect in terms of its layer dependence, indicating that it is highly sensitive to changes in inversion symmetry. Ferroelectric switching is demonstrated in field-effect transistor devices fabricated on ultrathin SnS films, in which a stronger ferroelectric response is achieved at negative gate voltages. Our work shows the promise of 2D SnS in ultrathin ferroelectric field-effect transistors as well as nanoscale electromechanical systems.

9.
J Phys Chem Lett ; 10(11): 2869-2873, 2019 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-31088074

RESUMO

Recently, some organic-inorganic hybrid perovskites (OIHPs) have been reported to exhibit strong subgap broadband luminescence. While the origin of such luminescence has been proposed by several groups, a strategy to prepare OIHP with the desired subgap emission properties has remained elusive. Here, we report controlled synthesis of a broadband-emitting single-crystal 2D OIHP with an average quantum yield of >80 %. We demonstrate that the intensity of broadband emission can be tuned by controlling the excess iodine ion concentration during the synthesis in hydroiodic acid. We show that the emitters exhibit characteristics of localized defects such as limited mobility and saturation at high excitation power. Using density functional theory calculations, we show that bond-state iodine interstitials are responsible for the observed long-lived luminescence.

10.
Nanoscale ; 11(7): 3186-3192, 2019 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-30723854

RESUMO

CsPb2Br5 is a new member of the all-inorganic lead halide perovskite family with unique structures and optoelectronic properties for various applications. As an indirect band gap semiconductor, the photoluminescence (PL) mechanism of CsPb2Br5 is still under debate. To resolve this issue, CsPb2Br5 microplates with strong green PL have been prepared by a hot-injection method. Characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD) analysis and ultraviolet-visible (UV-vis) absorption spectroscopy indicates the existence of a small amount of embedded CsPbBr3 phase. The removal of the embedded CsPbBr3 phase by treatment with water containing ethanol solvent resulted in complete PL quenching, suggesting the origin of PL due to the embedded CsPbBr3 phase. Spatially resolved PL and time-resolved PL mapping have been further employed to directly visualize the spatial distribution of different emission centers. Our single particle spectroscopic studies indicated the existence of three different emission centers with different PL lifetimes: two types of embedded CsPbBr3 phases (clumped and randomly distributed CsPbBr3 nanocrystals) and intrinsic defects of CsPb2Br5. The embedded CsPbBr3 phases with fast and intermediate PL lifetimes are the primary contributors to PL of the CsPb2Br5 microplates while their intrinsic defects with slow PL lifetimes make only a minor contribution. These studies have unambiguously clarified the PL mechanisms of the CsPb2Br5 microplates and provided the direct mapping of different emission centers, which resolve the contradictory explanation and debate about the PL mechanism of the CsPb2Br5 microplates.

11.
Nanoscale ; 11(7): 3216-3221, 2019 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-30706930

RESUMO

The grain size and quality of hybrid organic-inorganic perovskite (HOIP) films greatly affect the performance of perovskite solar cells (PSCs). However, dripping an anti-solvent during the spin coating process induces rapid nucleation and reduces the grain size. Here, a facile method is developed to engineer clusters in precursor solution and obtain high-quality perovskite films with an enlarged grain size. A cluster interfacial modifier, chlorobenzene (CB), is added to precursor solution. The modifier increases the interfacial energy between the precursor cluster and the solvent. The increased interfacial energy suppresses the nucleation and gives rise to HOIP films with large grains and high crystallinity. The efficiency of PSCs based on this method is greatly improved from 17.55% to 19.5%.

12.
Biotechnol Appl Biochem ; 66(3): 298-308, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30620086

RESUMO

Gibberellins (GAs) is one kind of important endogenous hormone in plants that regulates vegetative and reproductive growth of plants. GA2ox is a class of oxidase that plays a regulatory role in the third stage of GAs synthesis. In this paper, we cloned the GhGA2ox1 gene from an upland cotton (Gossypium hirsutum L. var. CCRI49). The results showed that the CDS of GhGA2ox1 is 996 bp, which encode 331 amino acids, which has high homology with GhGA2ox2 and NtGA2ox1. The quantitative real-time PCR showed that under the conditions of salt and drought stress, the expression of GhGA2ox1 had a higher upregulation in root, stem, and leaf of transgenic plant, compared with non-transgenic plant. Cotton plant that overexpressed the GhGA2ox1 gene showed higher drought and salt tolerance than non-transgenic cotton plant, and these results were supported by data of higher free proline, chlorophyll, and relative water content in transgenic plant compared with control plant. The expression level of antiretroviral genes, including GhEREB2, GhDREB1, GhWRKY5, and GhP5CS, was upregulated to varying degrees in transgenic plant. The above results indicate that overexpressed GhGA2ox1 gene can increases the tolerance to respond to drought and salt stress in upland cotton.


Assuntos
Secas , Giberelinas/biossíntese , Gossypium/enzimologia , Gossypium/genética , Oxirredutases/genética , Oxirredutases/metabolismo , Estresse Salino , Perfilação da Expressão Gênica , Regulação da Expressão Gênica de Plantas/genética , Oxirredutases/isolamento & purificação , Reação em Cadeia da Polimerase em Tempo Real
13.
Nanoscale ; 11(4): 1959-1967, 2019 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-30644957

RESUMO

Solution-processed organo-lead halide perovskites have emerged as promising optical gain media for tunable coherent light sources. The lasing performance is generally determined by the as-synthesized crystal quality. Noble metal nanostructures have been widely utilized to enhance optical responses due to their unique property of localized surface plasmon resonance. Herein, we report a simple method to enhance the near-infrared amplified spontaneous emission (ASE) performance of MAPbI3 polycrystalline films by solution-processing a PMMA spacer layer and an Au NR-doped PMMA top layer on perovskite thin films. As a result, the ASE threshold of the triple-layer perovskite film was significantly reduced by around 36% and the ASE intensity increased by 13.9-fold, compared to the pristine film. The underlying mechanism was attributed to the combined effects of surface passivation by PMMA and plasmon resonance enhancement of Au NRs. The passivation effect results in suppressing the nonradiative recombination and prolonging excited state decay, which have been investigated by transient absorption and pump-probe measurements. The plasmon effect is systematically studied through distance-dependent and spectra-dependent plasmon enhanced emission. The perovskite films with PMMA and Au NR coating showed great stability for 180 min under intense pulse laser continuous irradiation. The improved ASE performance still remained after leaving the film under the atmosphere for more than one month. We have successfully demonstrated a highly stable and sustained ASE output from MAPbI3 films under pulse laser excitation. This study provides a general approach for exploring plasmonic nanostructures in combination with polymers in the development and application of low-cost solution-processed semiconductor lasers.

14.
Angew Chem Int Ed Engl ; 58(10): 3077-3081, 2019 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-30311403

RESUMO

A persistent challenge in classical photocatalyst systems with extended light absorption is the unavoidable trade-off between maximizing light harvesting and sustaining high photoredox capability. Alternatively, cooperative energy conversion through photothermic activation and photocatalytic redox is a promising yet unmet scientific proposition that critically demands a spectrum-tailored catalyst system. Here, we construct a solar thermal-promoted photocatalyst, an ultrathin "biphasic" ordered-disordered D-HNb3 O8 junction, which performs two disparate spectral selective functions of photoexcitation by ordered structure and thermal activated conversion via disordered lattice for combinatorial photothermal mediated catalysis. This in situ synthetically immobilized lattice distortion, constrained to a single-entity monolayer structure not only circumvents interfacial incompatibility but also triggers near-field temperature rise at the catalyst-reactant complexes' proximity to promote photoreaction. Ultimately, a generic full solar conversion improvement for H2 fuel production, organic transformation and water purification is realized.

15.
Nanoscale ; 11(3): 1111-1122, 2019 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-30574647

RESUMO

Photoelectrochemical (PEC) water splitting represents a promising strategy to convert solar energy into chemical energy in the form of hydrogen, but its performance is severely limited by the sluggish water oxidation reaction. Herein, for the first time, we report the direct assembly of an ultrathin, uniform, and dense layer of Co3O4 on wormlike nanostructured hematite (WN-α-Fe2O3) to form a large-area and high-density WN-α-Fe2O3@Co3O4 core-shell nanoarray via in situ hydrothermal growth followed by calcination, in which the electrostatic force between WN-α-Fe2O3 and the reactants, pH- and temperature-controlled structures of WN-α-Fe2O3, and ultralow nucleation rate of Co3O4 precursors all play critical roles. The obtained heteronanostructure array shows a photocurrent density of 3.48 mA cm-2, which is 4.05 times higher than that of pristine WN-α-Fe2O3 (0.86 mA cm-2), an onset potential of ∼0.62 V, 60 mV lower than that of α-Fe2O3 (∼0.68 V), and a photoconversion efficiency of 0.55%, 3.93 times higher than that of WN-α-Fe2O3 (0.14%). This is among the highest performances reported for Fe2O3-based photoanodes for water splitting. It is discovered that the Co3O4 shells can significantly enhance the charge separation, accelerate the charge transport and transfer, and reduce the charge transfer resistance from the photoelectrode to the electrolyte for a fast water oxidation reaction, thereby greatly promoting the PEC water oxidation performance of pristine WN-α-Fe2O3. This work not only creates a novel low-cost and Earth-abundant WN-α-Fe2O3@Co3O4 photoelectrode with superior PEC water oxidation performance and provides scientific insights into the enhancement mechanism, but also offers a general strategy for the in situ growth of water oxidation catalysts on various photoelectrodes with 3-D complex geometries for PEC water splitting.

16.
J Phys Chem Lett ; 10(2): 183-188, 2019 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-30586995

RESUMO

Gold (Au) nanoparticles display enhanced near-infrared (NIR) photothermal effects upon the formation of clusters. We studied the photothermal properties of Au nanosphere clusters on the single-particle level using photothermal heterodyne imaging (PTHI) microscopy to understand the enhancement mechanisms. NIR photothermal responses of Au nanoparticle clusters were found to significantly increase from monomers to trimers. The averaged PTHI signal intensity of Au nanosphere dimers and trimers is ∼10 and ∼25 times that of monomers. The NIR photothermal effect of clustered nanospheres strongly correlates with their longitudinal plasmon mode. Clustered Au nanospheres were demonstrated to exhibit dual-capability NIR photothermal imaging and therapy of human prostate cancer cells with high efficiency and selectivity. This strategy can be potentially utilized for simultaneous cancer imaging and therapy with 3D selectivity.

17.
Nanoscale ; 11(1): 185-192, 2018 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-30525149

RESUMO

Two-photon excitation (2PE) photodynamic therapy (PDT) is a non-invasive technique for the treatment of cancer. However, its clinical applications are limited by small two-photon absorption cross section values of conventional photosensitizers. Here we designed multifunctional conjugated polymer based nanoparticles consisting of a conjugated polymer, a photosensitizer and a red-emitting dye, which can realize simultaneous 2PE red emission imaging and 2PE-PDT activities. The working principle is based on a 2PE fluorescence resonance energy transfer strategy from the conjugated polymer to photosensitizing and imaging agents. In these nanoparticles (NPs), the conjugated polymer, PPBF, was chosen as a two-photon light-harvesting material while the photosensitizer (tetraphenylporphyrin, TPP) and the red-emitting dye (TPD) were chosen as energy acceptors. The 2PE emission of TPP and TPD was enhanced by up to ∼161 and ∼23 times, respectively. The 2PE-PDT activity of these NPs was significantly improved compared with those NPs without PPBF by up to ∼149 times. Further surface-functionalization with folic acid (FA) groups allows these nanoparticles to exhibit selective affinity toward KB cancer cells. These NPs could act as novel 2PE conjugated polymer based nanoparticles combined with the advantages of low dark cytotoxicity, selective targeting and imaging-guided 2PE-PDT activities.


Assuntos
Nanopartículas/química , Neoplasias/terapia , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Polímeros/química , Animais , Linhagem Celular Tumoral , Sobrevivência Celular , Corantes/química , Transferência Ressonante de Energia de Fluorescência , Humanos , Lisossomos/química , Camundongos , Microscopia Eletrônica de Transmissão , Microscopia de Fluorescência , Células NIH 3T3 , Fótons , Porfirinas/química , Espécies Reativas de Oxigênio/metabolismo , Oxigênio Singlete/química
18.
ACS Appl Mater Interfaces ; 10(49): 42564-42572, 2018 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-30403343

RESUMO

In the past few years, substantial progress has been made in perovskite light-emitting devices. Both pure green and infrared thin-film perovskite light-emitting devices with external quantum efficiency over 20% have been successfully achieved. However, pure-red and blue thin-film perovskite light-emitting diodes still suffer from inferior efficiency. Therefore, the development of efficient and stable thin-film perovskite light-emitting diodes with pure-red and blue emissions is urgently needed for possible applications as a new display technology and solid-state lighting. Here, we demonstrate an efficient light-emitting diode with pure-red emission based on polymer-assisted in situ growth of high-quality all-inorganic CsPbBr0.6I2.4 perovskite nanocrystal films with homogenous distribution of nanocrystals with size 20-30 nm. With this method, we can dramatically reduce the formation temperature of CsPbBr0.6I2.4 and stabilize its perovskite phase. Eventually, we successfully demonstrate a pure-red-emission perovskite light-emitting diode with a high external quantum efficiency of 6.55% and luminance of 338 cd/m2. Furthermore, the device obtains an ultralow turn-on voltage of 1.5 V and a half-lifetime of over 0.5 h at a high initial luminance of 300 cd/m2.

19.
Nat Mater ; 17(10): 908-914, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-30202109

RESUMO

Due to their layered structure, two-dimensional Ruddlesden-Popper perovskites (RPPs), composed of multiple organic/inorganic quantum wells, can in principle be exfoliated down to few and single layers. These molecularly thin layers are expected to present unique properties with respect to the bulk counterpart, due to increased lattice deformations caused by interface strain. Here, we have synthesized centimetre-sized, pure-phase single-crystal RPP perovskites (CH3(CH2)3NH3)2(CH3NH3)n-1PbnI3n+1 (n = 1-4) from which single quantum well layers have been exfoliated. We observed a reversible shift in excitonic energies induced by laser annealing on exfoliated layers encapsulated by hexagonal boron nitride. Moreover, a highly efficient photodetector was fabricated using a molecularly thin n = 4 RPP crystal, showing a photogain of 105 and an internal quantum efficiency of ~34%. Our results suggest that, thanks to their dynamic structure, atomically thin perovskites enable an additional degree of control for the bandgap engineering of these materials.

20.
Nat Commun ; 9(1): 2335, 2018 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-29899332

RESUMO

Most two-dimensional (2D) covalent organic frameworks (COFs) are non-fluorescent in the solid state even when they are constructed from emissive building blocks. The fluorescence quenching is usually attributed to non-irradiative rotation-related or π-π stacking-caused thermal energy dissipation process. Currently there is a lack of guiding principle on how to design fluorescent, solid-state material made of COF. Herein, we demonstrate that the eclipsed stacking structure of 2D COFs can be used to turn on, and tune, the solid-state photoluminescence from non-emissive building blocks by the restriction of intramolecular bond rotation via intralayer and interlayer hydrogen bonds among highly organized layers in the eclipse-stacked COFs. Our COFs serve as a platform whereby the size of the conjugated linkers and side-chain functionalities can be varied, rendering the emission colour-tuneable from blue to yellow and even white. This work provides a guide to design new solid-state emitters using COFs.

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