Impact of Iron Incorporation on 2-4 nm Size Silicon Nanoparticles Properties

Iron-containing silicon nanoparticles were synthesized in an attempt to understand the effect of iron on the silicon nanoparticle (SiNP) photoluminescence and singlet-oxygen generation capacity. A wet chemical oxidation procedure of the sodium silicide precursor, obtained from the thermal treatment of a mixture of sodium, silicon, and an iron(III) organic salt under anaerobic conditions, was employed. Surface-oxidized and propylamine-terminated SiNPs were characterized using high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, time-resolved and steady-state photoluminescence, and time-correlated fluorescence anisotropy. On the basis of differences in the morphology, crystal structure, density, and photoluminescence spectrum, two distinct types of SiNPs were identified in a given synthesis batch: iron-free and iron-containing SiNPs. The results show that iron is inhomogeneously incorporated in the SiNPs leading to an efficient photoluminescence quenching. Emission arrives mainly from 2 nm size iron-free SiNPs. The nanoparticles were shown to generate singlet oxygen (1O2) upon 355 nm irradiation, though they were able to quench 1O2. Analysis of cytotoxicity using MTT assay on rat glioma C6 cells showed a strong dependence on the nature of the surface groups, as 100 μg/mL of propylamine-terminated iron-containing SiNPs leads to 85% decrease in cell viability while equal amounts of surface oxidized particles induced a 35% of cell death.Fil: Romero, Juan José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Wegmann, Marc. Friederich-Alexander University of Erlangen-Nuremberg; AlemaniaFil: Rodriguez, Hernan Bernardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Lillo, Rolando Cristian Rodrigo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Rubert, Aldo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Klein, Stefanie. Friederich-Alexander University of Erlangen-Nuremberg; AlemaniaFil: Kotler, Monica Lidia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; ArgentinaFil: Kryschi, Carola. Friederich-Alexander University of Erlangen-Nuremberg; AlemaniaFil: Gonzalez, Monica Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentin

Impact of Iron Incorporation on 2-4 nm Size Silicon Nanoparticles Properties

Iron-containing silicon nanoparticles were synthesized in an attempt to understand the effect of iron on the silicon nanoparticle (SiNP) photoluminescence and singlet-oxygen generation capacity. A wet chemical oxidation procedure of the sodium silicide precursor, obtained from the thermal treatment of a mixture of sodium, silicon, and an iron(III) organic salt under anaerobic conditions, was employed. Surface-oxidized and propylamine-terminated SiNPs were characterized using high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, time-resolved and steady-state photoluminescence, and time-correlated fluorescence anisotropy. On the basis of differences in the morphology, crystal structure, density, and photoluminescence spectrum, two distinct types of SiNPs were identified in a given synthesis batch: iron-free and iron-containing SiNPs. The results show that iron is inhomogeneously incorporated in the SiNPs leading to an efficient photoluminescence quenching. Emission arrives mainly from 2 nm size iron-free SiNPs. The nanoparticles were shown to generate singlet oxygen (1O2) upon 355 nm irradiation, though they were able to quench 1O2. Analysis of cytotoxicity using MTT assay on rat glioma C6 cells showed a strong dependence on the nature of the surface groups, as 100 μg/mL of propylamine-terminated iron-containing SiNPs leads to 85% decrease in cell viability while equal amounts of surface oxidized particles induced a 35% of cell death.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Facile Design of a Plasmonic Nanolaser

A spaser consists of a plasmonic noble-metal nanostructure that acts as nanocavity, when incorporated or surface-coupled two-level emitters constitute the nanoscale gain medium. Suited two-level emitters are, for instance, laser dyes. Optical pumping may provide efficient excitation energy transfer between the two-level emitters in the gain medium and the surface plasmons sustained in the nanocavity. Strong resonant coupling of the surface plasmon modes to the gain medium may establish an inherent feedback amplification mechanism which finally drives the spaser action. In this contribution, we demonstrate that spaser emission can be generated by amplifying longitudinal surface plasmon modes in gold nanorods by optically pumping surface-attached resonantly-coupled laser dyes. Therefore, we synthesized gold nanorods whose longitudinal surface plasmon resonance peak was adjusted between 680 and 700 nm. The gain medium was realized by electrostatically attaching the laser dye phthalocyanine tetrasulfonate via the positively-charged CTAB (cetyltrimethylammonium bromide) bilayer to the gold-nanorod surface. Phthalocyanine tetrasulfonate exhibits fluorescence at 700 nm. Fluorescence quenching experiments unambiguously gave indication of resonant excitation energy transfer. The fluorescence intensity ratio I0F/IF follows the Stern–Volmer relationship, and the Stern–Volmer coefficient was determined as KSV = 1.22 × 106 M−1. The spaser emission was observed in fs transient absorption spectra as an ultrafast decaying narrow emission peak around 716 nm

A facile one-pot synthesis of blue and red luminescent thiol stabilized gold nanoclusters: a thorough optical and microscopy study

Here in this contribution, blue and red luminescent 1-dodecanethiol (DT) terminated gold nanoclusters (AuNC) were prepared by a simple two-step synthesis route where the first step involved the surfactant-free synthesis of bare AuNC in N,N′-dimethylformamide (DMF) and the second step is the termination of the as-prepared bare AuNC by 1-dodecanethiol. The blue and red luminescent DT-terminated AuNC were isolated by a solvent-induced precipitation followed by an ultra-centrifugation technique. Both the bare AuNC and the blue and red luminescent DT-terminated AuNC exhibit stable photoluminescence and good solubility in various solvents. The photo-physical, electronic, structural, and morphological properties of the bare AuNC and the blue and red luminescent DT-terminated AuNC were examined by performing UV-Vis absorption spectroscopy, stationary and time-resolved PL spectroscopy, X-ray photoelectron spectroscopy (XPS), femtosecond transient absorption spectroscopy, Fourier-transform infrared spectroscopy (FTIR-ATR), and high-resolution transmission electron microscopy (HRTEM) experiments

A facile synthesis of highly stable and luminescent Ag clusters: a steady-state and time-resolved spectroscopy study

In this paper, we reported a very simple and environmentally friendly procedure for the synthesis of bright luminescent and nearly monodisperse Ag nanoclusters stabilized by a poly(N-vinylpyrrolidone) homopolymer. In this synthesis route acetonitrile or N,N-dimethylformamide (DMF) acts as both solvent and a reducing agent at their respective reflux temperatures. The as-prepared Ag clusters were found to be highly stable in various solvents as well as show nearly no changes in their emission intensity in solutions with different pH values and ionic strengths. Remarkably, the acetonitrile method predominantly produces blue emitting Ag clusters with a photoluminescence (PL) emission maximum at 424 nm (quantum yield 3.5%), whereas mainly blue-green emitting Ag clusters with the PL emission maximum at 450 nm (quantum yield 2.7%) were formed using the DMF method. The photo-physical, electronic, structural and morphological properties of the Ag clusters were investigated by performing UV/Vis absorption spectroscopy, stationary and time-resolved PL spectroscopy, X-ray photoelectron spectroscopy, femtosecond transient absorption spectroscopy, and transmission electron microscopy experiments

Caffeic Acid, Quercetin and 5-Fluorocytidine-Functionalized Au-Fe3O4 Nanoheterodimers for X-ray-Triggered Drug Delivery in Breast Tumor Spheroids

Au-Fe3O4 nanoheterodimers (NHD) were functionalized with the natural and synthetic anticancer drugs caffeic acid (CA), quercetin (Q) and 5-fluorocytidine (5FC). Their X-radiation dose-enhancing potential and chemotherapeutic efficacy for bimodal cancer therapy were investigated by designing multicellular tumor spheroids (MCTS) to in vitro avascular tumor models. MCTS were grown from the breast cancer cell lines MCF-7, MDA-MB-231, and MCF-10A. The MCF-7, MDA-MB-231 and MCF-10A MCTS were incubated with NHD-CA, NHD-Q, or NHD-5FC and then exposed to fractionated X-radiation comprising either a single 10 Gy dose, 2 daily single 5 Gy doses or 5 daily single 2 Gy doses. The NHD-CA, NHD-Q, and NHD-5FC affected the growth of X-ray irradiated and non-irradiated MCTS in a different manner. The impact of the NHDs on the glycolytic metabolism due to oxygen deprivation inside MCTS was assessed by measuring lactate secretion and glucose uptake by the MCTS. The NHD-CA and NHD-Q were found to act as X-radiation dose agents in MCF-7 MCTS and MDA-MB-231 MCTS and served as radioprotector in MCF-10A MCTS. X-ray triggered release of CA and Q inhibited lactate secretion and thereupon disturbed glycolytic reprogramming, whereas 5FC exerted their cytotoxic effects on both, healthy and tumor cells, after their release into the cytosol

Surface Functionalization and Electrical Discharge Sensitivity of Passivated Al Nanoparticles

Passivated aluminum nanoparticles are surface functionalized to elucidate their sensitivity against an electrical discharge. Two size fractions that differ in surface morphology are investigated. Electronic interactions between the partly inert, partly energetic organic molecules used for surface functionalization and the alumina surface are analyzed in detail. The nanoparticle surfaces are modified with the well-established, inert 2-[2-(2-methoxyethoxy)­ethoxy]­acetic acid, whereas energetic surface modification is achieved using 1,3,5-trinitroperhydro-1,3,5-triazine or the acidic and aromatic 2,4,6-trinitrophenol. A mechanistic model for the chemical surface functionalization of Al nanoparticles is hypothesized and corroborated by comprehensive optical and Fourier transform infrared spectroscopy studies. The surface structures are adjusted by developing a tunable stabilization procedure that prevents sedimentation and hence increases the saturation concentration in the liquid phase and finally affects the sensitivity character in view of electrical discharge ignition of dry powders. Detailed material characterization is conducted using transmission electron microscopy, combined with energy-dispersive X-ray spectroscopy and various absorption spectroscopy techniques (steady state in the infrared and ultraviolet/visible regime). The adjustment of surface structures of the distinct Al nanoparticle samples offers a valuable tool for tuning and tailoring the reactivity, sensitivity, stability, and energetic performances of the nanoparticles, and thereby enables the safe use of these multipurpose nanoparticles

ZnO superstructures via oriented aggregation initiated in a block copolymer melt

A fast and simple one pot synthesis of ZnO nano- and microparticles initiated and driven by an amino block copolymer O,O′-bis(2-aminopropyl)polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol (Jeffamine®) is reported. The specific building mechanism of ZnO mesocrystals is investigated in detail using electron microscopy and diffraction methods. Mesocrystals with a complex superstructure are formed as a result of a consecutive and oriented multiple stage aggregation process: first a 0D → 1D aggregation process is observed, then a 1D → 3D aggregation process occurs in which secondary particles form cones and multiple cone symmetries. Dots, rods, cones, and multiple cones have been isolated within a time resolved study which clearly supports the growth model. To control the morphology of the product particles, the influence of relevant synthesis parameters including stirring and sonication of the intermediate were investigated. Extensive surface characterization of the resulting mesocrystals is presented using infrared and photoluminescence spectroscopies as well as thermogravimetric analysis. Even after multiple washing steps, the particles exhibit a Jeffamine® coated surface that allows for easy dispersion in both polar and nonpolar solvents. The obtained mesocrystals efficiently scatter in the whole range of visible light

Antimony sulfide as a light absorber in highly ordered, coaxial nanocylindrical arrays: preparation and integration into a photovoltaic device

We demonstrate the preparation of functional 'extremely thin absorber' solar cells consisting of massively parallel arrays of nanocylindrical, coaxial n-TiO2/i-Sb2S3/p-CuSCN junctions. Anodic alumina is used as an inert template that provides ordered pores of 80 nm diameter and 1-50 mu m length. Atomic layer deposition (ALD) then coats pores of up to 20 mm with thin layers of the electron conductor and the intrinsic light absorber. The crystallization of the initially amorphous Sb2S3 upon annealing is strongly promoted by an underlying crystalline TiO2 layer. After the remaining pore volume is filled with the hole conductor by solution evaporation, the resulting coaxial p-i-n junctions display stable diode and photodiode electrical characteristics. A recombination timescale of 40 ms is extracted from impedance spectroscopy in open circuit conditions, whereas transient absorption spectroscopy indicates that holes are extracted from Sb2S3 with a lifetime of 1 ns