Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 27
Filtrar
Más filtros










Base de datos
Intervalo de año de publicación
1.
ACS Nano ; 17(20): 20366-20375, 2023 Oct 24.
Artículo en Inglés | MEDLINE | ID: mdl-37787507

RESUMEN

Nanocomposites are constructed from a matrix material combined with dispersed nanosized filler particles. Such a combination yields a powerful ability to tailor the desired mechanical, optical, electrical, thermodynamic, and antimicrobial material properties. Colloidal semiconductor nanocrystals (SCNCs) are exciting potential fillers, as they display size-, shape-, and composition-controlled properties and are easily embedded in diverse matrices. Here we present their role as quantum photoinitiators (QPIs) in acrylate-based polymer, where they act as a catalytic radical initiator and endow the system with mechanical, photocatalytic, and antimicrobial properties. By utilizing ZnO nanorods (NRs) as QPIs, we were able to increase the tensile strength and elongation at break of poly(ethylene glycol) diacrylate (PEGDA) hydrogels by up to 85%, unlike the use of the same ZnO NRs acting merely as fillers. Simultaneously, we endowed the PEGDA hydrogels with post-polymerization photocatalytic and antimicrobial activities and showed their ability to decompose methylene blue and significantly eradicate antibiotic-resistant bacteria and viral pathogens. Moreover, we demonstrate two fabrication showcase methods, traditional molding and digital light processing printing, that can yield hydrogels with complex architectures. These results position SCNC-based systems as promising candidates to act as all-in-one photoinitiators and fillers in nanocomposites for diverse biomedical applications, where specific and purpose-oriented characteristics are required.

2.
Nanoscale ; 14(5): 1944-1953, 2022 Feb 03.
Artículo en Inglés | MEDLINE | ID: mdl-35050298

RESUMEN

Semiconductor-metal hybrid nanostructures are promising materials for photocatalytic applications, providing high efficiencies compared to their composing counterparts. So far, the synthesis of such hybrid nanoparticles was limited to batch reactors, achieving tunability while demonstrating how each of the nanocrystals' characteristics affects photocatalytic performances. Yet, new methodologies should be established to increase the synthetic yield while maintaining high control over the resulting structures. Herein, scalable advanced flow techniques are introduced, yielding ZnSe-metal hybrid nanoparticles either in a thermal growth or photo-induced growth regime. Firstly, thermal gold growth in the flow reactor is achieved with good control over the metal tip size and the nanoparticle morphology. We address the dependence of the reaction on temperature, the precursor to nanorod molar ratios, and additional parameters. Additionally, light-induced growth by the flow reactor is demonstrated for platinum clusters. The quality of the resulting hybrids is directly demonstrated by their functionality in photocatalytic hydrogen generation by water reduction, displaying enhanced activity compared to bare ZnSe nanorods. The fairly straightforward adaptation of such powerful flow-reaction techniques to scale-up photocatalytic hybrid nanoparticle syntheses takes them one step forwards towards the realization of their potential in real-life application scenarios.

3.
ACS Appl Mater Interfaces ; 14(1): 647-653, 2022 Jan 12.
Artículo en Inglés | MEDLINE | ID: mdl-34958193

RESUMEN

Hybrid semiconductor-metal nanocrystals manifest efficient photocatalytic activity related to the metal domain promoting charge carrier separation and providing an active catalytic site. The surface properties of such nanoparticles are also of paramount importance in determining their photocatalytic activity. Addressing the combination of surface effects in catalysis on metals, with the electronic properties of hybrid nanoparticles, we examined the effect of coating CdS-Au hybrid nanoparticles with sulfide, an anion that is expected to bind strongly to both domains, on the photocatalytic functionality. Upon sulfide coating, one-electron processes - namely the oxidative production of hydroxyl radicals and the reductive production of superoxide - were increased, whereas the activity for two-electron reduction processes - H2 and hydrogen peroxide generation - was hampered. These findings indicate a double-edged sword effect for sulfide coating that on one side relieves the hole extraction bottleneck from the semiconductor segment and, on the other hand, poisons the metal domain restricting its reductive capacity for the two-electron processes requiring a chemisorption step on the metal surface. The work further demonstrates the importance of surface properties for the photocatalytic action of such hybrid nanoparticle systems.

4.
J Am Chem Soc ; 143(47): 19816-19823, 2021 12 01.
Artículo en Inglés | MEDLINE | ID: mdl-34791875

RESUMEN

Coupled colloidal quantum dot (CQD) dimers represent a new class of artificial molecules composed of fused core/shell semiconductor nanocrystals. The electronic coupling and wave function hybridization are enabled by the formation of an epitaxial connection with a coherent lattice between the shells of the two neighboring quantum dots where the shell material and its dimensions dictate the quantum barrier characteristics for the charge carriers. Herein we introduce a colloidal approach to control the neck formation at the interface between the two CQDs in such artificial molecular constructs. This allows the tailoring of the neck barrier in prelinked homodimers formed via fusion of multifaceted wurtzite CdSe/CdS CQDs. The effects of reaction time, temperature, and excess ligands are studied. The neck filling process follows an intraparticle ripening mechanism at relatively mild reaction conditions while avoiding interparticle ripening. The degree of surface ligand passivation plays a key role in activating the surface atom diffusion to the neck region. The degree of neck filling strongly depends also on the initial relative orientation of the two CQDs, where homonymous plane attachment allows for facile neck growth, unlike the case of heteronymous plane attachment. Upon neck filling, the observed red-shift of the absorption and fluorescence measured both for ensemble and single dimers is assigned to enhanced hybridization of the confined wave function in CQD dimer molecules, as supported by quantum calculations. The fine-tuning of the particle interface introduced herein provides therefore a powerful tool to further control the extent of hybridization and coupling in CQD molecules.

5.
Angew Chem Int Ed Engl ; 60(26): 14467-14472, 2021 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-33793047

RESUMEN

Top-down fabricated nanoantenna architectures of both metallic and dielectric materials show powerful functionalities for Raman and fluorescence enhancement with relevance to single molecule sensing while inducing directionality of chromophore emission with implications for single photon sources. We synthesize the smallest bow-tie nanoantenna by selective tip-to-tip fusion of two tetrahedral colloidal quantum dots (CQDs) forming a dimer. While the tetrahedral monomers emit non-polarized light, the bow-tie architecture manifests nanoantenna functionality of enhanced emission polarization along the bow-tie axis, as predicted theoretically and revealed by single-particle spectroscopy. Theory also predicts the formation of an electric-field hotspot at the bow-tie epicenter. This is utilized for selective light-induced photocatalytic metal growth at that location, unlike growth on the free tips in dark conditions, thus demonstrating bow-tie dimer functionality as a photochemical reaction center.

6.
Nanoscale ; 13(15): 7152-7160, 2021 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-33889919

RESUMEN

Semiconductor nanocrystal based photoinitiators, quantum PIs, are a viable alternative to organic photoinitiators demonstrating unique advantages, including a broad and tunable excitation window, limited migration, and more. Aiming towards efficient quantum PIs with tunable properties, a deeper understanding of the relationships between the nanoparticle properties and their efficiency is required. Herein, we studied the morphological effect on ZnO nanocrystals functioning as photoinitiators in both water-based and solvent-free formulations by comparing rod and pyramidal shaped particles of similar volumes and nearly identical surface area. Superior polymerization performances are measured for the nanorods. Photocatalytic characterization including oxygen consumption and reactive oxygen species formation as well as dyes reduction and oxidation, also showed enhanced activities for the nanorods. The different performances were attributed to the anisotropic nanorod morphology which is beneficial for charge separation as well as to the presence of a reactive [0001] facet in the nanorods, which is known to increase the adsorption of molecular oxygen and anionic molecules, thus affecting the catalytic activity. These observations, along with the higher photoinitiation efficiency of the ZnO nanorods, bring them closer to functionality as photoinitiators in numerous photopolymerization applications.

7.
J Am Chem Soc ; 143(2): 577-587, 2021 01 20.
Artículo en Inglés | MEDLINE | ID: mdl-33353293

RESUMEN

Semiconductor nanocrystals are promising photocatalysts for a wide range of applications, ranging from alternative fuel generation to biomedical and environmental applications. This stems from their diverse properties, including flexible spectral tunability, stability, and photocatalytic efficiencies. Their functionality depends on the complex influence of multiple parameters, including their composition, dimensions, architecture, surface coating, and environmental conditions. A particularly promising direction for rapid adoption of these nanoparticles as photocatalysts is their ability to act as photoinitiators (PIs) for radical polymerization. Previous studies served to demonstrate the proof of concept for the use of quantum confined semiconductor nanocrystals as photoinitiators, coining the term Quantum PIs, and provided insights for their photocatalytic mechanism of action. However, these early reports suffered from low efficiencies while requiring purging with inert gases, use of additives, and irradiation by high light intensities with very long excitation durations, which limited their potential for real-life applications. The progress in nanocrystal syntheses and surface engineering has opened the way to the introduction of the next generation of Quantum PIs. Herein, we introduce the research area of nanocrystal photocatalysts, review their studies as Quantum PIs for radical polymerization, from suspension polymerization to novel printing, as well as in a new family of polymerization techniques, of reversible deactivation radical polymerization, and provide a forward-looking view for the challenges and prospects of this field.

8.
Atherosclerosis ; 313: 144-149, 2020 11.
Artículo en Inglés | MEDLINE | ID: mdl-33049656

RESUMEN

BACKGROUND AND AIMS: Parasympathetic dysfunction is associated with increased risk for major adverse cardiovascular events (MACE). However, clinically validated biomarkers that reflect parasympathetic activity are not yet available. We sought to assess the ability of serum cholinesterase activity to predict long term survival in patients undergoing coronary angiography. METHODS: We prospectively followed 1002 consecutive patients undergoing clinically indicated coronary angiography (acute coronary syndrome or stable angina). We measured blood acetylcholinesterase (AChE) activity using the acetylcholine analog acetylthiocholine. Mortality rates were determined up to 10 years of follow-up. We divided our cohort into 3 groups with low, intermediate and high AChE activity by a Chi-square automatic interaction detection method (CHAID). RESULTS: Patients with lower than cutoff levels of AChE (<300 nmol/min/ml) had higher mortality rates over 10 years of follow-up, after adjusting for conventional risk factors, biomarkers, clinical indication, and use of medications (HR = 1.6, 95% CI 1.1-2.5, p = 0.02). Patients with intermediate levels of AChE (300-582 nmol/min/ml) were also at increased risk for death (HR = 1.4, 95% CI 1.1-1.9, p = 0.02). AChE was inversely correlated with C-reactive protein, troponin I, fibrinogen and neutrophil/lymphocyte ratio levels. CONCLUSIONS: Patients presenting for coronary angiography with low levels of serum AChE activity are at increased risk for death during long term follow-up.


Asunto(s)
Acetilcolinesterasa , Enfermedad de la Arteria Coronaria , Biomarcadores , Angiografía Coronaria , Enfermedad de la Arteria Coronaria/diagnóstico por imagen , Humanos , Pronóstico , Estudios Prospectivos , Factores de Riesgo
9.
J Control Release ; 318: 145-157, 2020 02.
Artículo en Inglés | MEDLINE | ID: mdl-31830540

RESUMEN

Quantum dots offer superior optical features and hold a great potential as an imaging tool in comparison to 'conventional' fluorescent dyes. However, in vivo application in inflammatory-associated disorders is limited due to potential toxicity following systemic administration. Vascular inflammation contributes to cardiovascular diseases such as restenosis (re-narrowing of the artery following angioplasty), and poor prognosis is associated with the increased number of monocytes-derived macrophages (MDMs) in the arterial wall. Local administration of a suitable delivery system targeting MDMs could provide effective fluorescent imaging while minimizing systemic exposure and toxicity. We report here on the physicochemical characteristics and the structural stability of MDMs-targeted liposomal QDs (LipQDs), cellular uptake and cytotoxicity, the systemic biodistribution of LipQDs following local intra-luminal administration of LipQDs in carotid-injured rats vs. systemic administration, and imaging of QDs in the arterial tissue. The local treatment with LipQDs was found to be a suitable approach for targeting QDs to MDMs in the injured artery. In contrast to free QDs, the LipQDs formulation exhibited unique properties including structural and fluorescent stability, increased accumulation and retention for up to 24 h, and targeting properties enabling imaging of MDMs. MDMs imaging by targeted nanoparticles (NPs) could potentially serve for the detection of MDMs density in the injured artery for diagnostic purposes.


Asunto(s)
Puntos Cuánticos , Animales , Arterias , Liposomas , Macrófagos , Ratas , Distribución Tisular
10.
Nat Commun ; 10(1): 5401, 2019 12 16.
Artículo en Inglés | MEDLINE | ID: mdl-31844043

RESUMEN

Coupling of atoms is the basis of chemistry, yielding the beauty and richness of molecules. We utilize semiconductor nanocrystals as artificial atoms to form nanocrystal molecules that are structurally and electronically coupled. CdSe/CdS core/shell nanocrystals are linked to form dimers which are then fused via constrained oriented attachment. The possible nanocrystal facets in which such fusion takes place are analyzed with atomic resolution revealing the distribution of possible crystal fusion scenarios. Coherent coupling and wave-function hybridization are manifested by a redshift of the band gap, in agreement with quantum mechanical simulations. Single nanoparticle spectroscopy unravels the attributes of coupled nanocrystal dimers related to the unique combination of quantum mechanical tunneling and energy transfer mechanisms. This sets the stage for nanocrystal chemistry to yield a diverse selection of coupled nanocrystal molecules constructed from controlled core/shell nanocrystal building blocks. These are of direct relevance for numerous applications in displays, sensing, biological tagging and emerging quantum technologies.

11.
Nano Lett ; 19(9): 5844-5852, 2019 09 11.
Artículo en Inglés | MEDLINE | ID: mdl-31424944

RESUMEN

The majority of developed and approved anticancer nanomedicines have been designed to exploit the dogma of the enhanced permeability and retention (EPR) effect, which is based on the leakiness of the tumor's blood vessels accompanied by impeded lymphatic drainage. However, the EPR effect has been under scrutiny recently because of its variable manifestation across tumor types and animal species and its poor translation to human cancer therapy. To facilitate the EPR effect, systemically injected NPs should overcome the obstacle of rapid recognition and elimination by the mononuclear phagocyte system (MPS). We hypothesized that circulating monocytes, major cells of the MPS that infiltrate the tumor, may serve as an alternative method for achieving increased tumor accumulation of NPs, independent of the EPR effect. We describe here the accumulation of liposomal quantum dots (LipQDs) designed for active delivery via monocytes, in comparison to LipQDs designed for passive delivery (via the EPR effect), following IV administration in a mammary carcinoma model. Hydrophilic QDs were synthesized and entrapped in functionalized liposomes, conferring passive ("stealth" NPs; PEGylated, neutral charge) and active (monocyte-mediated delivery; positively charged) properties by differing in their lipid composition, membrane PEGylation, and charge (positively, negatively, and neutrally charged). The various physicochemical parameters affecting the entrapment yield and optical stability were examined in vitro and in vivo. Biodistribution in the blood, various organs, and in the tumor was determined by the fluorescence intensity and Cd analyses. Following the treatment of animals (intact and mammary-carcinoma-bearing mice) with disparate formulations of LipQDs (differing by their lipid composition, neutrally and positively charged surfaces, and hydrophilic membrane), we demonstrate comparable tumor uptake of QDs delivered by the passive and the active routes (mainly by Ly-6Chi monocytes). Our findings suggest that entrapping QDs in nanosized liposomal formulations, prepared by a new facile method, imparts superior structural and optical stability and a suitable biodistribution profile leading to increased tumor uptake of fluorescently stable QDs.


Asunto(s)
Liposomas/farmacología , Neoplasias Mamarias Animales/tratamiento farmacológico , Sistema Mononuclear Fagocítico/química , Puntos Cuánticos/química , Animales , Vasos Sanguíneos/efectos de los fármacos , Línea Celular Tumoral , Sistemas de Liberación de Medicamentos , Femenino , Humanos , Interacciones Hidrofóbicas e Hidrofílicas/efectos de los fármacos , Lípidos/química , Lípidos/farmacología , Liposomas/química , Neoplasias Mamarias Animales/patología , Ratones , Nanomedicina , Células Neoplásicas Circulantes , Permeabilidad/efectos de los fármacos
12.
Nanoscale ; 11(23): 11209-11216, 2019 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-31157812

RESUMEN

Semiconductor nanocrystals have been shown to have unique advantages over traditional organic photoinitiators for polymerization in solution. However, efficient photoinitiation with such nanoparticles in solvent-free and additive-free formulations so far has not been achieved. Herein, the ability to use semiconductor nanocrystals for efficient bulk polymerization as sole initiators is reported, operating under modern UV-blue-LED light sources found in 3D printers and other photocuring applications. Hybrid semiconductor-metal nanorods exhibit superior photoinitiation capability to their pristine semiconductor counterparts, attributed to the enhanced charge separation and oxygen consumption in such systems. Moreover, photoinitiation by semiconductor nanocrystals overcoated by inorganic ligands is reported, thus increasing the scope of possible applications and shedding light on the photoinitiation mechanism; in light of the results, two possible pathways are discussed - ligand-mediated and cation-coordinated oxidation. A demonstration of the unique attributes of the quantum photoinitiators is reported in their use for high-resolution two-photon printing of optically fluorescing microstructures, demonstrating a multi-functionality capability. The bulk polymerization demonstrated here can be advantageous over solvent based methods as it alleviates the need of post-polymerization drying and reduces waste and exposure to toxic solvents, as well as broadens the possible use of quantum photoinitiators for industrial and research uses.

13.
Nat Commun ; 10(1): 2, 2019 01 02.
Artículo en Inglés | MEDLINE | ID: mdl-30602734

RESUMEN

Semiconductor heterostructure nanocrystals, especially with core/shell architectures, are important for numerous applications. Here we show that by decreasing the shell growth rate the morphology of ZnS shells on ZnSe quantum rods can be tuned from flat to islands-like, which decreases the interfacial strain energy. Further reduced growth speed, approaching the thermodynamic limit, leads to coherent shell growth forming unique helical-shell morphology. This reveals a template-free mechanism for induced chirality at the nanoscale. The helical morphology minimizes the sum of the strain and surface energy and maintains band gap emission due to its coherent core/shell interface without traps, unlike the other morphologies. Reaching the thermodynamic controlled growth regime for colloidal semiconductor core/shell nanocrystals thus offers morphologies with clear impact on their applicative potential.

14.
Adv Mater ; 30(41): e1706697, 2018 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-29656489

RESUMEN

Hybrid semiconductor-metal nanoparticles (HNPs) manifest unique combined and often synergetic properties stemming from the materials combination. These structures exhibit spatial charge separation across the semiconductor-metal junction upon light absorption, enabling their use as photocatalysts. So far, the main impetus of photocatalysis research in HNPs addresses their functionality in solar fuel generation. Recently, it was discovered that HNPs are functional in efficient photocatalytic generation of reactive oxygen species (ROS). This has opened the path for their implementation in diverse biomedical and industrial applications where high spatially temporally resolved ROS formation is essential. Here, the latest studies on the synergistic characteristics of HNPs are summarized, including their optical, electrical, and chemical properties and their photocatalytic function in the field of solar fuel generation is briefly discussed. Recent studies are then focused concerning photocatalytic ROS formation with HNPs under aerobic conditions. The emergent applications of this capacity are then highlighted, including light-induced modulation of enzymatic activity, photodynamic therapy, antifouling, wound healing, and as novel photoinitiators for 3D-printing. The superb photophysical and photocatalytic properties of HNPs offer already clear advantages for their utility in scenarios requiring on-demand light-induced radical formation and the full potential of HNPs in this context is yet to be revealed.


Asunto(s)
Puntos Cuánticos , Animales , Catálisis , Humanos , Procesos Fotoquímicos , Puntos Cuánticos/química
15.
Nano Lett ; 17(7): 4497-4501, 2017 07 12.
Artículo en Inglés | MEDLINE | ID: mdl-28617606

RESUMEN

Additive manufacturing processes enable fabrication of complex and functional three-dimensional (3D) objects ranging from engine parts to artificial organs. Photopolymerization, which is the most versatile technology enabling such processes through 3D printing, utilizes photoinitiators that break into radicals upon light absorption. We report on a new family of photoinitiators for 3D printing based on hybrid semiconductor-metal nanoparticles. Unlike conventional photoinitiators that are consumed upon irradiation, these particles form radicals through a photocatalytic process. Light absorption by the semiconductor nanorod is followed by charge separation and electron transfer to the metal tip, enabling redox reactions to form radicals in aerobic conditions. In particular, we demonstrate their use in 3D printing in water, where they simultaneously form hydroxyl radicals for the polymerization and consume dissolved oxygen that is a known inhibitor. We also demonstrate their potential for two-photon polymerization due to their giant two-photon absorption cross section.

16.
Langmuir ; 33(22): 5519-5526, 2017 06 06.
Artículo en Inglés | MEDLINE | ID: mdl-28497974

RESUMEN

Carbon nanotubes (CNTs) and semiconductor nanocrystals (SCNCs) are known to be interesting donor-acceptor partners due to their unique optical and electronic properties. These exciting features have led to the development of novel composites based on these two nanomaterials and to their characterization for use in various applications, such as components in sensors, transistors, solar cells and biomedical devices. Two approaches based on covalent and noncovalent methods have been suggested for coupling the SCNCs to CNTs. Most covalent conjugation methods used so far were found to disrupt the electronic structure of the CNTs or interfere with charge transfer in the CNT-SCNC interface. Moreover, it offers random and poorly organized nanoparticle coatings. Therefore, noncovalent methods are considered to be ideal for better electronic coupling. However, a key common drawback of noncovalent methods is the lack of stability which hampers their applicability. In this article, a method has been developed to couple semiconductor seeded nanorods onto CNTs through π-π interactions. The CNTs and pyrene conjugated SCNC hybrid materials were characterized by both microscopic and spectroscopic techniques. Fluorescence and photocurrent measurements suggest the proposed pi-stacking approach results in a strong electronic coupling between the CNTs and the SCNCs leading to better photocurrent efficiency than that of a covalent conjugation method reported using similar SCNC material. Overall, the CNT-SCNC films reported in the present study open the scope for the fabrication of optoelectronic devices for various applications.

17.
ACS Nano ; 11(3): 3038-3051, 2017 03 28.
Artículo en Inglés | MEDLINE | ID: mdl-28196324

RESUMEN

Quantum dots (QDs), semiconductor nanocrystals, are fluorescent nanoparticles of growing interest as an imaging tool of a diseased tissue. However, a major concern is their biocompatibility, cytotoxicity, and fluorescence instability in biological milieu, impeding their use in biomedical applications, in general, and for inflammation imaging, in particular. In addition, for an efficient fluorescent signal at the desired tissue, and avoiding systemic biodistribution and possible toxicity, targeting is desired. We hypothesized that phagocytic cells of the innate immunity system (mainly circulating monocytes) can be exploited as transporters of specially designed liposomes containing QDs to the inflamed tissue. We developed a liposomal delivery system of QDs (LipQDs) characterized with high encapsulation yield, enhanced optical properties including far-red emission wavelength and fluorescent stability, high quantum yield, and protracted fluorescent decay lifetime. Treatment with LipQDs, rather than free QDs, exhibited high accumulation and retention following intravenous administration in carotid-injured rats (an inflammatory model). QD-monocyte colocalization was detected in the inflamed arterial segment only following treatment with LipQDs. No cytotoxicity was observed following LipQD treatment in cell cultures, and changes in liver enzymes and gross histopathological changes were not detected in mice and rats, respectively. Our results suggest that the LipQD formulation could be a promising strategy for imaging inflammation.


Asunto(s)
Sistemas de Liberación de Medicamentos , Inflamación/diagnóstico por imagen , Monocitos/química , Monocitos/metabolismo , Imagen Óptica , Puntos Cuánticos/química , Animales , Compuestos de Cadmio/química , Células Cultivadas , Liposomas/química , Liposomas/farmacocinética , Masculino , Ratones , Ratones Endogámicos BALB C , Células RAW 264.7 , Ratas , Ratas Endogámicas , Compuestos de Selenio/química , Sulfuros/química , Distribución Tisular , Compuestos de Zinc/química
18.
Nano Lett ; 16(7): 4266-73, 2016 07 13.
Artículo en Inglés | MEDLINE | ID: mdl-27224678

RESUMEN

Semiconductor-metal hybrid nanoparticles manifest efficient light-induced spatial charge separation at the semiconductor-metal interface, as demonstrated by their use for hydrogen generation via water splitting. Here, we pioneer a study of their functionality as efficient photocatalysts for the formation of reactive oxygen species. We observed enhanced photocatalytic activity forming hydrogen peroxide, superoxide, and hydroxyl radicals upon light excitation, which was significantly larger than that of the semiconductor nanocrystals, attributed to the charge separation and the catalytic function of the metal tip. We used this photocatalytic functionality for modulating the enzymatic activity of horseradish peroxidase as a model system, demonstrating the potential use of hybrid nanoparticles as active agents for controlling biological processes through illumination. The capability to produce reactive oxygen species by illumination on-demand enhances the available peroxidase-based tools for research and opens the path for studying biological processes at high spatiotemporal resolution, laying the foundation for developing novel therapeutic approaches.


Asunto(s)
Luz , Nanopartículas del Metal , Especies Reactivas de Oxígeno/química , Semiconductores , Fenómenos Biológicos , Peroxidasa de Rábano Silvestre/química
19.
Nanoscale ; 7(45): 19193-200, 2015 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-26526222

RESUMEN

Semiconductor nanocrystals exhibit unique fluorescence properties which are tunable in size, shape and composition. The high quantum yield and enhanced stability have led to their use in biomedical imaging and flat panel displays. Here, semiconductor nanorod based inkjet inks are presented, overcoming limitations of the commonly reported quantum dots in printing applications. Fluorescent seeded nanorods were found to be outstanding candidates for fluorescent inks, due to their low particle-particle interactions and negligible self-absorption. This is manifested by insignificant emission shifts upon printing, even in highly concentrated printed layers and by maintenance of a high fluorescence quantum yield, unlike quantum dots which exhibit fluorescence wavelength shifts and quenching effects. This behavior results from the reduced absorption/emission overlap, accompanied by low energy transfer efficiencies between the nanorods as supported by steady state and time resolved fluorescence measurements. The new seeded nanorod inks enable patterning of thin fluorescent layers, for demanding light emission applications such as signage and displays.

20.
ACS Appl Mater Interfaces ; 7(38): 21107-14, 2015 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-26334672

RESUMEN

Singlet oxygen ((1)O2) generated upon photostimulation of photosensitizer molecules is a highly reactive specie which is utilized in photodynamic therapy. Recent studies have shown that semiconductor nanoparticles can be used as donors in fluorescence resonance energy transfer (FRET) process to excite attached photosensitizer molecules. In these studies, their unique properties, such as low nanoscale size, long-term photostability, wide broad absorbance band, large absorption cross section, and narrow and tunable emission bands were used to provide advantages over the traditional methods to produce singlet oxygen. Previous studies that achieved this goal, however, showed some limitations, such as low FRET efficiency, poor colloidal stability, nonspecific interactions, and/or complex preparation procedure. In this work, we developed and characterized a novel system of semiconductor quantum rods (QRs) and the photosensitizer meso-tetra(hydroxyphenyl) chlorin (mTHPC), as a model system that produces singlet oxygen without these limitations. A simple two-step preparation method is shown; Hydrophobic CdSe/CdS QRs are solubilized in aqueous solutions by encapsulation with lecithin and PEGylated phospholipid (PEG-PL) of two lipid lengths: PEG350 or PEG2000. Then, the hydrophobic photosensitizer mTHPC, was intercalated into the new amphiphilic PEG-PL coating of the QR, providing a strong attachment to the nanoparticle without covalent linkage. These PEGylated QR (eQR)-mTHPC nanocomposites show efficient FRET processes upon light stimulation of the QR component which results in efficient production of singlet oxygen. The results demonstrate the potential for future use of this concept in photodynamic therapy schemes.


Asunto(s)
Transferencia Resonante de Energía de Fluorescencia , Fosfolípidos/química , Fármacos Fotosensibilizantes/química , Polietilenglicoles/química , Puntos Cuánticos/química , Fluorescencia , Cinética , Mesoporfirinas/química , Nanocompuestos/química , Puntos Cuánticos/ultraestructura , Oxígeno Singlete/química
SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA
...