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1.
Nano Lett ; 17(9): 5607-5613, 2017 09 13.
Artigo em Inglês | MEDLINE | ID: mdl-28776995

RESUMO

Auger recombination is a nonradiative three-particle process wherein the electron-hole recombination energy dissipates as a kinetic energy of a third carrier. Auger decay is enhanced in quantum-dot (QD) forms of semiconductor materials compared to their bulk counterparts. Because this process is detrimental to many prospective applications of the QDs, the development of effective approaches for suppressing Auger recombination has been an important goal in the QD field. One such approach involves "smoothing" of the confinement potential, which suppresses the intraband transition involved in the dissipation of the electron-hole recombination energy. The present study evaluates the effect of increasing "smoothness" of the confinement potential on Auger decay employing a series of CdSe/CdS-based QDs wherein the core and the shell are separated by an intermediate layer of a CdSexS1-x alloy comprised of 1-5 sublayers with a radially tuned composition. As inferred from single-dot measurements, use of the five-step grading scheme allows for strong suppression of Auger decay for both biexcitons and charged excitons. Further, due to nearly identical emissivities of neutral and charged excitons, these QDs exhibit an interesting phenomenon of lifetime blinking for which random fluctuations of a photoluminescence lifetime occur for a nearly constant emission intensity.

2.
Nano Lett ; 17(4): 2319-2327, 2017 04 12.
Artigo em Inglês | MEDLINE | ID: mdl-28253617

RESUMO

Typical use of colloidal quantum dots (QDs) as bright, tunable phosphors in real applications relies on engineering of their surfaces to suppress the loss of excited carriers to surface trap states or to the surrounding medium. Here, we explore the utility of QDs in an application that actually exploits their propensity toward photoionization, namely within efficient and robust photocathodes for use in next-generation electron guns. In order to establish the relevance of QD films as photocathodes, we evaluate the efficiency of electron photoemission of films of a variety of compositions in a typical electron gun configuration. By quantifying photocurrent as a function of excitation photon energy, excitation intensity and pulse duration, we establish the role of hot electrons in photoemission within the multiphoton excitation regime. We also demonstrate the effect of QD structure and film deposition methods on efficiency, which suggests numerous pathways for further enhancements. Finally, we show that QD photocathodes offer superior efficiencies relative to standard copper cathodes and are robust against degradation under ambient conditions.

3.
Nano Lett ; 17(3): 1787-1795, 2017 03 08.
Artigo em Inglês | MEDLINE | ID: mdl-28169547

RESUMO

Quantum dots (QDs) of ternary I-III-VI2 compounds such as CuInS2 and CuInSe2 have been actively investigated as heavy-metal-free alternatives to cadmium- and lead-containing semiconductor nanomaterials. One serious limitation of these nanostructures, however, is a large photoluminescence (PL) line width (typically >300 meV), the origin of which is still not fully understood. It remains even unclear whether the observed broadening results from considerable sample heterogeneities (due, e.g., to size polydispersity) or is an unavoidable intrinsic property of individual QDs. Here, we answer this question by conducting single-particle measurements on a new type of CuInS2 (CIS) QDs with an especially thick ZnS shell. These QDs show a greatly enhanced photostability compared to core-only or thin-shell samples and, importantly, exhibit a strongly suppressed PL blinking at the single-dot level. Spectrally resolved measurements reveal that the single-dot, room-temperature PL line width is much narrower (down to ∼60 meV) than that of the ensemble samples. To explain this distinction, we invoke a model wherein PL from CIS QDs arises from radiative recombination of a delocalized band-edge electron and a localized hole residing on a Cu-related defect and also account for the effects of electron-hole Coulomb coupling. We show that random positioning of the emitting center in the QD can lead to more than 300 meV variation in the PL energy, which represents at least one of the reasons for large PL broadening of the ensemble samples. These results suggest that in addition to narrowing size dispersion, future efforts on tightening the emission spectra of these QDs might also attempt decreasing the "positional" heterogeneity of the emitting centers.

4.
J Am Chem Soc ; 139(19): 6644-6653, 2017 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-28431206

RESUMO

The use of semiconductor nanocrystal quantum dots (QDs) in optoelectronic devices typically requires postsynthetic chemical surface treatments to enhance electronic coupling between QDs and allow for efficient charge transport in QD films. Despite their importance in solar cells and infrared (IR) light-emitting diodes and photodetectors, advances in these chemical treatments for lead chalcogenide (PbE; E = S, Se, Te) QDs have lagged behind those of, for instance, II-VI semiconductor QDs. Here, we introduce a method for fast and effective ligand exchange for PbE QDs in solution, resulting in QDs completely passivated by a wide range of small anionic ligands. Due to electrostatic stabilization, these QDs are readily dispersible in polar solvents, in which they form highly concentrated solutions that remain stable for months. QDs of all three Pb chalcogenides retain their photoluminescence, allowing for a detailed study of the effect of the surface ionic double layer on electronic passivation of QD surfaces, which we find can be explained using the hard/soft acid-base theory. Importantly, we prepare highly conductive films of PbS, PbSe, and PbTe QDs by directly casting from solution without further chemical treatment, as determined by field-effect transistor measurements. This method allows for precise control over the surface chemistry, and therefore the transport properties of deposited films. It also permits single-step deposition of films of unprecedented thickness via continuous processing techniques, as we demonstrate by preparing a dense, smooth, 5.3-µm-thick PbSe QD film via doctor-blading. As such, it offers important advantages over laborious layer-by-layer methods for solar cells and photodetectors, while opening the door to new possibilities in ionizing-radiation detectors.

5.
Nano Lett ; 16(4): 2349-62, 2016 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-26882294

RESUMO

Organic-inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs-Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral and dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton-exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs-Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the "universal volume scaling" previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. This points toward the need for the development of approaches for effective suppression of Auger recombination in these nanomaterials, using perhaps insights gained from previous studies of II-VI nanocrystals.

6.
Nat Methods ; 8(5): 393-9, 2011 May.
Artigo em Inglês | MEDLINE | ID: mdl-21527931

RESUMO

Two-photon excitation of fluorescent proteins is an attractive approach for imaging living systems. Today researchers are eager to know which proteins are the brightest and what the best excitation wavelengths are. Here we review the two-photon absorption properties of a wide variety of fluorescent proteins, including new far-red variants, to produce a comprehensive guide to choosing the right fluorescent protein and excitation wavelength for two-photon applications.


Assuntos
Proteínas Luminescentes/química , Fótons , Espectrofotometria/métodos , Lasers , Proteínas Luminescentes/genética , Microscopia Confocal/métodos , Proteínas Recombinantes/química , Proteínas Recombinantes/genética , Eletricidade Estática
7.
J Phys Chem A ; 118(21): 3749-3759, 2014 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-24785544

RESUMO

We study instantaneous two-photon absorption (2PA) in a series of nominally quasi-centrosymmetric trans-bis(tributylphosphine)-bis-(4-((9,9-diethyl-7-ethynyl-9H-fluoren-2-yl) ethynyl)-R)-platinum complexes, where 11 different substituents, R = N(phenyl)2(NPh2), NH2, OCH3, t-butyl, CH3, H, F, CF3, CN, benzothiazole, and NO2, represent a range of electron-donating (ED) and electron-withdrawing (EW) strengths, while the Pt core acts as a weak ED group. We measure the 2PA cross section in the 540-810 nm excitation wavelength range by complementary femtosecond two-photon excited fluorescence (2PEF) and nonlinear transmission (NLT) methods and compare the obtained values to those of the Pt-core chromophore and the corresponding noncentrosymmetric side group (ligand) chromophores. Peak 2PA cross sections of neutral and ED-substituted Pt complexes occur at S0 → Sn transitions to higher energy states, above the lowest-energy S0 → S1 transition, and the corresponding values increase systematically with increasing ED strength, reaching maximum value, σ2 ∼ 300 GM (1 GM = 10-50 cm4 s), for R = NPh2. At transition energies overlapping with the lowest-energy S0 → S1 transition in the one-photon absorption (1PA) spectrum, the same neutral and ED-substituted Pt complexes show weak 2PA, σ2 < 30-100 GM, which is in agreement with the nearly quadrupolar structure of these systems. Surprisingly, EW-substituted Pt complexes display a very different behavior, where the peak 2PA of the S0 → S1 transition gradually increases with increasing EW strength, reaching values σ2 = 700 GM for R = NO2, while in the S0 → Sn transition region the peak 2PEF cross section decreases. We explained this effect by breaking of inversion symmetry due to conformational distortions associated with low energy barrier for ground-state rotation of the ligands. Our findings are corroborated by theoretical calculations that show large increase of the permanent electric dipole moment change in the S0 → S1 transition when ligands with strong EW substituents are twisted by 90° relative to the planar chromophore. Our NLT results in the S0 → S1 transition region are quantitatively similar to those obtained from the 2PEF measurement. However, at higher transition energy corresponding to S0 → Sn transition region, the NLT method yields effective multiphoton absorption stronger than the 2PEF measurement in the same systems. Such enhancement is observed in all Pt complexes as well as in all ligand chromophores studied, and we tentatively attribute this effect to nearly saturated excited-state absorption (ESA), which may occur if 2PA from the ground state is immediately followed by strongly allowed 1PA to higher excited states.

8.
J Chem Phys ; 138(21): 214314, 2013 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-23758378

RESUMO

We compare the two-photon absorption (2PA) spectra of non-centrosymmetrical metal-free tribenzo-tetraazachlorin (H2TBTAC) and analogous symmetrical tetra-tert-butyl-phthalocyanine (H2TtBuPc). Surprisingly, despite formal lack of center of inversion, the 2PA spectrum of H2TBTAC displays a two-photon allowed transition at 935 nm, similar to gerade-gerade (g-g) transitions observed in H2TtBuPc and in other symmetrical phthalocyanines. This transition is even better resolved in the singlet-singlet excited-state absorption spectrum. We tentatively explain the survival of the g-g transition in H2TBTAC by assuming that the main π-electron conjugation pathway in the tetraaza-substituted tetrapyrrole macrocycle bypasses the outer parts of the two oppositely located isoindole rings and thus renders the optically responsive core of the chromophore quasi-centrosymmetrical. By using the independently measured ground- and excited-state absorption extinction coefficients, we also show that the two-photon absorptivity can be quantitatively explained by a simple three-level model with the lowest energy Q1 state serving as an intermediate level.


Assuntos
Fótons , Porfirinas/química , Conformação Molecular , Análise Espectral
9.
Phys Chem Chem Phys ; 14(33): 11743-52, 2012 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-22828583

RESUMO

A series of bis(arylidene)cycloalkanone compounds based on cyclobutanone, cyclopentanone, cyclohexanone and cycloheptanone, C4-C7, respectively, with a D-π-A-π-D structure containing the same donor and acceptor but different alicyclic rings was prepared. The effects of alicyclic ring size on the photophysical, photochemical and electrochemical properties of these compounds were investigated systematically. We found that an increase of the number of carbons in the central alicyclic ring leads to changes in geometry, which has significant effects on the conjugation, and photophysical and photochemical properties. These effects include decreases in the fluorescence quantum yield, transient lifetimes, peak extinction coefficients, and the singlet oxygen quantum yield with the increase of the ring size. The one-photon absorption spectra, the two-photon absorption (2PA) spectra, and the fluorescence spectra all show a hypsochromic shift with increasing ring size. The results of this study provide guidance for the design of new cycloketone-based D-π-A-π-D 2PA compounds for photopolymerization and photodynamic therapy applications.

10.
Phys Chem Chem Phys ; 14(44): 15299-307, 2012 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-23051920

RESUMO

Spectroscopic properties, two-photon absorption (TPA) and excited state absorption (ESA), of two organic cyanine dyes and of a ruthenium based organometallic cyanine are compared in order to rationalize their similar ns-optical power limiting (OPL) efficiency in the telecommunication wavelength range. The TPA contribution to the ns-OPL behavior is higher for both organic cyanines, while the main process is a TPA-induced ESA in the case of the organometallic system, in which the ruthenium induces a broadening of the NIR-ESA band and resulting in a strong spectral overlap between TPA and ESA spectra.


Assuntos
Carbocianinas/química , Corantes/química , Compostos Organometálicos/química , Estrutura Molecular , Rutênio/química , Espectrofotometria
11.
J Phys Chem A ; 116(15): 3781-93, 2012 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-22429020

RESUMO

We have performed a study of the one- and two-photon absorption properties of a systematically varied series of triarylamino-compounds with one, two, or three attached diarylborane arms arranged in linear dipolar, bent dipolar, and octupolar geometries. Two-photon fluorescence excitation spectra were measured over a wide spectral range with femtosecond laser pulses. We found that on going from the single-arm to the two- and three-arm systems, the peak in two-photon absorption (2PA) cross-section is suppressed by factors of 3-11 for the lowest excitonic level associated with the electronic coupling of the arms, whereas it is enhanced by factors of 4-8 for the higher excitonic level. These results show that the coupling of arms redistributes the 2PA cross-section between the excitonic levels in a manner that strongly favors the higher-energy excitonic level. The experimental data on one- and two-photon cross-sections, ground- and excited-state transition dipole moments, and permanent dipole moment differences between the ground and the lowest excited states were compared to the results obtained from a simple Frenkel exciton model and from highly correlated quantum-chemical calculations. It has been found that planarization of the structure around the triarylamine moiety leads to a sizable increase in peak 2PA cross-section for the lowest excitonic level of the two-arm system, whereas for the three-arm system, the corresponding peak was weakened and shifted to lower energy. Our studies show the importance of the interarm coupling, number of arms, and structural planarity on both the enhancement and the suppression of two-photon cross-sections in multiarm molecules.


Assuntos
Aminas/química , Elétrons , Boranos , Lasers , Fótons , Análise Espectral
12.
ACS Appl Mater Interfaces ; 14(26): 29679-29689, 2022 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-35729115

RESUMO

While luminescent solar concentrators (LSCs) have been researched for several decades, there is still a lack of commercially available systems, mostly due to scalability, performance, aesthetics, or some combination of these challenges. These obstacles can be overcome by the systematic optimization of a laminated glass LSC design, demonstrated herein. In particular, we first show that it is possible to improve optical and electrical efficiencies of an LSC by fine-tuned optimization of the constituent fluorophore-containing interlayer resin. Further still, an increased understanding of commercially available solar cells allows us to establish a direct correlation between the device's optical and electrical efficiency. Next, optical characterization of LSCs of varying sizes allows us to elucidate the main loss mechanisms in our LSCs, as well as ways to mitigate them. Altogether these optimization steps create opportunities for high-performance multi-interlayer LSC devices with demonstrated electrical power conversion efficiency as high as 1.1% to 4.9% at visual light transmission of 74% to 5%. Furthermore, careful examination of different blue-color (red-band absorbing) dyes provides a path for color-tunability of LSC windows toward neutral regimes. Design iterations of multiple device form factors enabled a color-neutral prototype without significant performance losses by separating color-neutralizing and LSC layers into different panes of an insulated glass unit. This work demonstrates the importance of LSC design optimization in achieving high-performance solar window technology with commercially acceptable aesthetics.

13.
Front Chem ; 10: 988227, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36339045

RESUMO

The spectral quality of sunlight reaching plants remains a path for optimization in greenhouse cultivation. Quantum dots represent a novel, emission-tunable luminescent material for optimizing the sunlight spectrum in greenhouses with minimal intensity loss, ultimately enabling improved light use efficiency of plant growth without requiring electricity. In this study, greenhouse films containing CuInS2/ZnS quantum dots were utilized to absorb and convert ultraviolet and blue photons from sunlight to a photoluminescent emission centered at 600 nm. To analyze the effects of the quantum dot film spectrum on plant production, a 25-week tomato trial was conducted in Dutch glass greenhouses. Plants under the quantum dot film experienced a 14% reduction in overall daily light integral, resulting from perpendicular photosynthetically active radiation transmission of 85.3%, mainly due to reflection losses. Despite this reduction in intensity, the modified sunlight spectrum and light diffusion provided by the quantum dot film gave rise to 5.7% improved saleable production yield, nearly identical total fruiting biomass production, 23% higher light use efficiency (g/mol), 10% faster vegetative growth rate, and 36% reduced tomato waste compared to the control, which had no additional films. Based on this result, materials incorporating quantum dots show promise in enabling passive, electricity-free spectrum modification for improving crop production in greenhouse cultivation, but extensive controlled crop studies are needed to further validate their effectiveness.

14.
BMC Biotechnol ; 11: 20, 2011 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-21366923

RESUMO

BACKGROUND: Multiphoton microscopy (MPM) offers many advantages over conventional wide-field and confocal laser scanning microscopy (CLSM) for imaging biological samples such as 3D resolution of excitation, reduced phototoxicity, and deeper tissue imaging. However, adapting MPM for critical multi-color measurements presents a challenge because of the largely overlapping two-photon absorption (TPA) peaks of common biological fluorophores. Currently, most multi-color MPM relies on the absorbance at one intermediate wavelength of multiple dyes, which introduces problems such as decreased and unequal excitation efficiency across the set of dyes. RESULTS: Here we describe an MPM system incorporating two, independently controlled sources of two-photon excitation whose wavelengths are adjusted to maximally excite one dye while minimally exciting the other. We report increased signal-to-noise ratios and decreased false positive emission bleed-through using this novel multiple-excitation MPM (ME-MPM) compared to conventional single-excitation MPM (SE-MPM) in a variety of multi-color imaging applications. CONCLUSIONS: Similar to the tremendous gain in popularity of CLSM after the introduction of multi-color imaging, we anticipate that the ME-MPM system will further increase the popularity of MPM. In addition, ME-MPM provides an excellent tool to more rapidly design and optimize pairs of fluorescence probes for multi-color two-photon imaging, such as CFP/YFP or GFP/DsRed for CLSM.


Assuntos
Microscopia de Fluorescência por Excitação Multifotônica/métodos , Animais , Linhagem Celular , Células/metabolismo , Humanos , Sensibilidade e Especificidade
15.
Chemistry ; 17(8): 2479-91, 2011 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-21264958

RESUMO

The synthesis, one-photon photophysics and two-photon absorption (2PA) of three dipolar D-π-A 4-[9,9-di(2-ethylhexyl)-7-diphenylaminofluoren-2-yl]-2,2':6',2''-terpyridine and their platinum chloride complexes with different linkers between the donor and acceptor are reported. All ligands exhibit (1)π,π* transition in the UV and (1)π,π*/(1)ICT (intramolecular charge transfer) transition in the visible regions, while the complexes display a lower-energy (1)π,π*/(1)CT (charge transfer) transition in the visible region in addition to the high-energy (1)π,π* transitions. All ligands and the complexes are emissive at room temperature and 77 K, with the emitting excited state assigned as the mixed (1)π,π* and (1)CT states at RT. Transient absorption from the ligands and the complexes were observed. 2PA was investigated for all ligands and complexes. The two-photon absorption cross-sections (σ(2)) of the complexes (600-2000 GM) measured by Z-scan experiment are much larger than those of their corresponding ligands measured by the two-photon induced fluorescence method. The ligand and the complex with the ethynylene linker show much stronger 2PA than those with the vinylene linker.


Assuntos
Fluorenos/química , Modelos Moleculares , Compostos Organoplatínicos/síntese química , Fótons , Compostos de Platina/química , Piridinas/química , Fluorenos/síntese química , Luminescência , Estrutura Molecular , Compostos Organoplatínicos/química , Processos Fotoquímicos , Piridinas/síntese química
16.
J Phys Chem A ; 115(17): 4255-62, 2011 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-21456577

RESUMO

We investigate two-photon absorption (2PA) in a series of fluorenyl-based 9,9-diethyl-2-ethynyl-7-((4-R-phenyl)ethynyl)-9,9a-dihydro-4aH-fluorene chromophores with R being various electron donating (ED) and electron withdrawing (EW) groups. We use wavelength-tunable femtosecond laser pulses to measure the 2PA cross sections in the lowest dipole-allowed transition and show that the substituents with stronger ED or EW character enhance the peak 2PA cross section (up to σ(2) ∼ 60-80 GM) while the neutral substituents lead to smaller cross sections, σ(2) < 10 GM. We apply two-level approximation to establish a quantitative relation between the 2PA in the pure electronic transition (0-0) and the corresponding change of the permanent electric dipole moment upon the excitation (Δµ). This relation is elucidated by comparing Δµ values obtained from the 2PA measurements with quantum-chemical calculations and with measurements of solvatochromic shifts in a series of solvents. We show that the calculated Δµ correlate well with the values obtained from the 2PA spectroscopy. The Δµ values obtained from the solvatochromic shifts agree well with the above two methods for the chromophores with neutral or weak EW or ED substituents. On the other hand, stronger EW or ED end groups give much larger Stokes shifts, which lead to an overestimation of the Δµ values. We tentatively attribute this effect to the excitation-induced electronic density change occurring predominantly at the substituent side of the molecule, which causes the effective point dipole associated with the Δµ to interact more strongly with the surrounding solvent.


Assuntos
Elétrons , Fluorenos/química , Fótons , Estrutura Molecular
17.
BMC Biotechnol ; 10: 6, 2010 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-20122267

RESUMO

BACKGROUND: Two-photon dual-color imaging of tissues and cells labeled with fluorescent proteins (FPs) is challenging because most two-photon microscopes only provide one laser excitation wavelength at a time. At present, methods for two-photon dual-color imaging are limited due to the requirement of large differences in Stokes shifts between the FPs used and their low two-photon absorption (2PA) efficiency. RESULTS: Here we present a new method of dual-color two-photon microscopy that uses the simultaneous excitation of the lowest-energy electronic transition of a blue fluorescent protein and a higher-energy electronic transition of a red fluorescent protein. CONCLUSION: Our method does not require large differences in Stokes shifts and can be extended to a variety of FP pairs with larger 2PA efficiency and more optimal imaging properties.


Assuntos
Proteínas Luminescentes/química , Microscopia de Fluorescência por Excitação Multifotônica/métodos , Corantes Fluorescentes/química , Proteína Vermelha Fluorescente
18.
ACS Appl Bio Mater ; 3(12): 8567-8574, 2020 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-35019627

RESUMO

Near-infrared (NIR) emitting quantum dots (QDs) with emission in the biological transparency windows (NIR-I: 650-950 nm and NIR-II: 1000-1350 nm) are promising candidates for deep-tissue bioimaging. However, they typically contain toxic heavy metals such as cadmium, mercury, arsenic, or lead. We report on the biocompatibility of high brightness CuInSexS2-x/ZnS (CISeS/ZnS) QDs with a tunable emission covering the visible to NIR (550-1300 nm peak emission) and quantify the transmission of their photoluminescence through multiple biological components to evaluate their use as imaging agents. In general, CISeS/ZnS QDs were less cytotoxic to mouse fibroblast cells when compared with commercial CdSe/ZnS and InP/ZnS QDs. Surprisingly, InP/ZnS QDs significantly upregulated expression of apoptotic genes in mouse fibroblast cells, while cells exposed to CISeS/ZnS QDs did not. These findings provide insight into biocompatibility and cytotoxicity of CISeS/ZnS QDs that could be used for bioimaging.

19.
Org Biomol Chem ; 7(5): 889-96, 2009 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-19225671

RESUMO

We have investigated the photophysical properties and intracellular behaviour of a series of hydrophilic conjugated porphyrin dimers. All the dimers exhibit intense linear absorption at 650-800 nm and high singlet oxygen quantum yields (0.5-0.9 in methanol), as required for an efficient sensitiser for photodynamic therapy (PDT). They also exhibit fluorescence at 700-800 nm, with fluorescence quantum yields of up to 0.13 in methanol, and show extremely large two-photon absorption maxima of 8,000-17,000 GM in the near-IR. The dimers aggregate in aqueous solution, but aggregation is reduced by binding to bovine serum albumin (BSA), as manifested by an increase in fluorescence intensity and a sharpening in the emission bands. This process can be regarded as a model for the interaction with proteins under physiological conditions. Confocal fluorescence microscopy of live cells was used to monitor the rate of cellular uptake, intracellular localisation and photostability. Porphyrin dimers with positively charged substituents partition into cells more efficiently than the negatively charged dimers. The photostability of these dimers, in living cells, is significantly better than that of the clinical photosensitiser verteporfin. Analysis of the photophysical parameters and intracellular imaging data indicates that these dimers are promising candidates for one-photon and two-photon excited PDT.


Assuntos
Fotoquimioterapia/métodos , Porfirinas/síntese química , Animais , Células/metabolismo , Células Cultivadas , Dimerização , Humanos , Raios Infravermelhos , Fótons , Fármacos Fotossensibilizantes/síntese química , Porfirinas/farmacocinética , Solubilidade
20.
ACS Nano ; 13(8): 9112-9121, 2019 08 27.
Artigo em Inglês | MEDLINE | ID: mdl-31291097

RESUMO

While luminescent concentrators (LCs) are mainly designed to harvest sunlight and convert its energy into electricity, the same concept can be advantageous in alternative applications. Examples of such applications are demonstrated here by coupling the edge-guided light of high-performance LCs based on CuInSexS2-x/ZnS quantum dots into optical fibers with emission covering visible-to-NIR spectral regions. In particular, a cost-efficient, miniature broadband light source for medical diagnostics, a spectral-conversion and light-guiding device for agriculture, and a large-area broadband tunable detector for telecommunications are demonstrated. Various design considerations and performance optimization approaches are discussed and summarized. Prototypes of the devices are manufactured and tested. Individual elements of the broadband light source show coupling efficiencies up to 1%, which is sufficient to saturate typical fiber-coupled spectrometers at a minimal integration time of 1 ms using 100 mW blue excitation. Agricultural devices are capable of delivering ∼10% of photosynthetically active radiation (per device) converted from absorbed sunlight to the lower canopy of plants, which boosted the tomato yield in a commercial greenhouse by 7% (fresh weight). Finally, large-scale prototype detectors can be used to discern time-modulated unfocused signals with an average power as low as 1 µW, which would be useful for free-space telecommunication systems. Fully optimized devices are expected to make significant impacts on speed and bandwidth of free-space telecommunication systems, medical diagnostics, and greenhouse crop yields.


Assuntos
Fibras Ópticas , Pontos Quânticos/química , Energia Solar , Telecomunicações/tendências , Agricultura/tendências , Técnicas de Laboratório Clínico/tendências , Humanos , Iluminação , Luminescência , Pontos Quânticos/uso terapêutico , Refratometria , Luz Solar
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