Synthesis of Eu(III): naphtoyltrifluoroacetone:trioctylphosphineoxide complex-doped silica fluorescent nanoparticles through a new approach

In this study, a new approach for the preparation of a fluorescent europium(III) complex-doped silica nanoparticles has been developed. The synthesis process involved the following steps: (1) preparing silica nanoparticles by water-in-oil microemulsion method, (2) dyeing the spherical silica particles by europium(III): naphtoyltrifluoroacetone (NTA):trioctylphosphineoxide (TOPO), (3) adsorbing polyvinylpyrrolidone (PVP) onto the core structure and growing silica on PVP surface. The as-prepared nanoparticles exhibited stronger emission intensity, higher photo- and chemical stability. Despite the fact that europium(III) complex was doped into the nanoparticles, its fluorescence properties such as a wide Stokes shift, a narrow emission peak, and long fluorescence lifetime, were retained. The nanoparticles are uniform in shape and size (50 ± 5 nm in diameter). This study could provide new avenue for the fabrication of Eu: NTA:TOPO-based nanoparticles, facilitating their application in bioassay issues.     

Structure of manganese zinc ferrite spinel nanoparticles prepared with co-precipitation in reversed microemulsions

The structure of Mn_0.5Zn_0.5Fe₂O₄ spinel ferrite nanoparticles is studied as a function of their size and the experimental conditions of their synthesis using X-ray absorption spectroscopy. The nanoparticles of different sizes down to approximately 2 nm and with a narrow size distribution were synthesized using co-precipitation in reverse microemulsions. Simultaneous refinement of the X-ray absorption fine structure (EXAFS) of three constituting metals shows a migration of Mn and Zn ions to the octahedral site of the spinel lattice compensated by the corresponding migration of the Fe ions. To a smaller extent, Mn ions switch the occupation site already in bulk and in larger nanoparticles, while a sporadic migration of Zn is detected only in the nanoparticles with sizes below approximately 5 nm. X-ray absorption near edge structure (XANES) reveals considerable variations in the position of the Mn K edge, suggesting the average Mn valence in the nanoparticles to be higher than 3+. Annealing at 500 °C relaxes the structure of as-synthesized nanoparticles toward the structure of the ceramic bulk standard. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Regenerative synthesis of copper nanoparticles by?photoirradiation

Copper nanoparticles have attracted much attention because of their low cost, and because their use can contribute toward the sustainability of metal resources. In this study, copper nanoparticles were synthesized by the photoirradiation of copper acetate solution at room temperature. The diameter and chemical composition of the obtained copper nanoparticles were analyzed using field-emission scanning electron microscope (FE-SEM) spectrophotometer and an X-ray photoelectron spectrometer. Well-dispersed copper nanoparticles with  ~5 nm in diameter were observed in the solution. On the other hand, when the nanoparticle solution was exposed to fresh air, nanoparticles were not observed in the solution. Furthermore, the copper nanoparticles were recovered from a solution of decomposed nanoparticles by re-photoirradiation.     

Preparation of nanosized metal (oxides) by gas phase hydrolysis using mesoporous materials as nanoreactors

Immobilized nanosized metal (oxides) on carbonaceous carriers were prepared by hydrolysis under mild conditions by using the carrier pores as a kind of nanoreactor. Metal alkoxide vapor was adsorbed on the carrier and then formed the product upon exposure to water vapor. With this facile method, Titania, Vanadia, Rhodium (oxide), and Platinum (oxide) nanostructures were prepared at high yields, high loadings, and good dispersion in the carrier material. High number concentrations of spheroidal nanoparticles of uniform size (diameter ca. 5 nm) were obtained from less reactive precursors, whereas with highly reactive precursors, such nanoparticles occurred only after subsequent calcination. Nanoparticles appeared to be the thermodynamically stable form of the metal (oxide) produced in the pores. Highly reactive precursors formed metastable seeds, which nucleated and restructured into nanoparticles upon subsequent exposure to heat. The presented method allows for preparation of metal (oxide) nanostructures and effective control of their size and shape.     

Nanometric core-shell-shell γ-Fe2O3/SiO2/TiO2 particles

The preparation of core-shell-shell γ-Fe₂O₃/SiO₂/TiO₂ nanoparticles of few tens nanometers is performed by successively coating onto magnetic nanoparticles a SiO₂ layer and a TiO₂ layer, using sol–gel methods. The thickness of the two layers and the aggregation state of the particles can be controlled by the experimental conditions used for the two coatings. These composite nanoparticles may find application as magnetic photocatalysts, since they are characterized by their small diameters which allow a good accessibility to the TiO₂ shell. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Study on Synthesis of Silver Nanoparticles Using dsDNA as Template and Detection of GSH

In this work, silver nanoparticles are synthesized using a simple and sensitive method by using double-stranded DNA (dsDNA-Ag NPs) as a template. The prepared dsDNA-Ag NPs are characterized by fluorescence spectroscopy analysis, X-ray photoelectron spectroscopy analysis, and transmission electron microscopy analysis. The excitation wavelength of the prepared silver nanoparticles is 295 nm, the emission wavelength is 377 nm, the average particle size is 11.2 nm, and the dispersion is uniform with pleasurable stability. The nanomaterials are used as fluorescent probes to detect glutathione (GSH). After adding glutathione to the dsDNA-Ag NPs fluorescent probes, the fluorescence of dsDNA-Ag NPs is burst due to electron transfer and S Ag bond generation, and the linear range of detection concentration is 0–90 mm with a detection limit of 0.37 mm .     

Laser-Scanning Microscopy for Electrophoretic Mobility Characterization of Single Nanoparticles

To enable detailed studies of interactions between nanoparticles and their environment and the correlations between various nanoparticle properties, one must go beyond ensemble averages and toward single-particle measurements. However, current methodologies for the single-nanoparticle analysis of charge and size either lack the flexibility to study dynamic processes on the single-particle level or are highly specific and require complex microfluidic devices. In addition, accurate measurements of the electrophoretic mobility (or zeta-potential) based on the optical detection of single nanoparticles remain challenging due to the low photon budget, the required sampling frequency, and the fact that electroosmosis in typical microfluidic devices must be analyzed carefully. In this study, a method is investigated to accurately characterize the electrophoretic mobility of individual nanoparticles and estimate their size by simultaneously analyzing the electrokinetic- and Brownian motion in a simple microfluidic channel. Fast laser scanning excitation and sensitive detection of fluorescent photons enable single-nanoparticle velocimetry experiments in an oscillating electric field at high frame rates.     

The influence of metal ion on the scaling in the mineral water tests

Finding some economical and environmentally friendly inhibitors was always one of our research goals. The present paper researched the method of rapid controlled precipitation (RCP) and the results showed it was reliable and suitable as the method of evaluating the scaling. Then through the method of RCP, the paper would investigate four kinds of metal ions as the inhibitors, the results showed the zinc ion and copper ion were suitable as the inhibitors. In the 300-mL solution (calcium ion concentration of 126.5 mg L⁻¹), the total efficiency of 100% was reached for the copper ion concentration of 0.8 mg L⁻¹ and for the zinc ion concentration of 0.3 mg L⁻¹. After choosing the zinc ion and copper ion as the inhibitors, this paper also investigated the cooperative effect of the mixed metal ions, the results showed the mixed ions would not change the inhibition effectiveness of any single metal ion, but could affect the calcium carbonate germination and change the crystal morphology. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Detection of carcinoembryonic antigen using functional magnetic and fluorescent nanoparticles in magnetic separators

We combined a sandwich immunoassay, anti-CEA/CEA/anti-CEA, with functional magnetic (~80 nm) and fluorescent (~180 nm) nanoparticles in magnetic separators to demonstrate a detection method for carcinoembryonic antigen (CEA). Determination of CEA in serum can be used in clinical diagnosis and monitoring of tumor-related diseases. The CEA concentrations in samples were deduced and determined based on the reference plot using the measured fluorescent intensity of sandwich nanoparticles from the sample. The linear range of CEA detection was from 18 ng/mL to 1.8 pg/mL. The detection limit of CEA was 1.8 pg/mL. In comparison with most other detection methods, this method had advantages of lower detection limit and wider linear range. The recovery was higher than 94%. The CEA concentrations of two serum samples were determined to be 9.0 and 55 ng/mL, which differed by 6.7% (9.6 ng/mL) and 9.1% (50 ng/mL) from the measurements of enzyme-linked immunosorbent assay (ELISA), respectively. The analysis time can be reduced to one third of ELISA. This method has good potential for other biomarker detections and biochemical applications.     

Incorporation of Siderophore Binding Sites in a Dipodal Fluorescent Sensor for Fe(III)

A new fluorescent probe 3, has been developed for the detection of Fe(III) in water based samples. The design of 3 involved the incorporation of Fe(III) binding sites observed in naturally occurring Siderophores into a synthetic sensing assembly. The probe, containing two Schiff base receptors connected to a mesitylene platform, was prepared in two steps. The dipodal sensor displayed good selectivity for Fe(III) when tested against other physiological and environmentally important metal ions, in HEPES buffered solution at pH 7.0, through a quenching of the fluorescent intensity. Stern-Volmer analysis of this quenching interaction indicated a 1:1 (host : guest) binding stoichiometry between the probe and Fe(III). The association constant, K _a calculated using the Benesi-Hildebrand equation was found to be 3.8 × 10⁴ M⁻¹. Crucially, the sensor was capable of measuring Fe(III) competitively in solutions containing both Fe(III) and Cu(II). Thus, the adoption of Fe(III) binding sites found in nature, into synthetic luminescent assemblies has proven an effective design strategy for the development of new Fe(III) probes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Layered double hydroxide nanoparticles incorporating terbium: applicability as a fluorescent probe and morphology modifier

Stable and non-invasive fluorescent probes for nanotoxicological investigations are greatly needed to track the fate of nanoparticles in biological systems. The potential for terbium (Tb) to act as a fluorescent probe and its effect on layered double hydroxide (LDH) nanoparticle morphology are presented in this study. Incorporation of Tb during synthesis offers a simple methodology to easily tailor LDH nanoparticle thickness. A three-fold reduction in the average crystallite thickness (from 13 to 4 nm) has been achieved, whilst preferential lateral growth of LDH nanoparticles in the a-b crystal plane has been observed with increasing Tb loadings. Remarkably, Tb–LDH nanoparticles have emitted green fluorescence with a fluorescence quantum yield of 0.044.     

Growth kinetics and long-term stability of CdS nanoparticles in aqueous solution under ambient conditions

The ubiquity of naturally occurring nanoparticles in the aquatic environment is now widely accepted, but a better understanding of the conditions that promote their formation and persistence is needed. Using cadmium sulfide (CdS) as a model metal sulfide species, thiolate-capped CdS nanoparticles were prepared in the laboratory to evaluate how aquatic conditions influence metal sulfide nanoparticle growth and stability. This work examines CdS nanoparticle growth directly in aqueous solution at room temperature by utilizing the size-dependent spectroscopic properties of semiconductors detectable by UV/vis. CdS nanoparticle growth was governed by oriented attachment, a non-classical mechanism of crystallization in which small precursor nanoparticles coalesce to form larger nanoparticle products. Nanoparticle growth was slowed with increasing capping agent and decreasing ionic strength. In addition to examining the short-term (hours) growth of the nanoparticles, a long-term study was conducted in which cysteine-capped CdS nanoparticles were monitored over 3 weeks in solutions of various ionic strengths. The long-term study revealed an apparent shift from small nanoparticles to nanoparticles twice their original size, suggesting nanoparticle growth may continue through oriented attachment over longer time scales. High-ionic strength solutions resulted in salt-induced aggregation and eventual settling of nanoparticles within days, whereas low-ionic strength solutions were stable against settling over the course of the experiment. Sulfide recovery from cysteine-capped CdS nanoparticles as acid volatile sulfide was nearly quantitative after 2 weeks in fully oxygenated water, demonstrating significantly slowed oxidation of sulfide when complexed to Cd(II) within CdS nanoparticles. The nanoparticles were also shown to be resistant to oxidation by Fe(III) (hydr)oxide. This study illustrates that aggregation, rather than chemical oxidation, is likely more important to the lifetime of many metal sulfide nanoparticles in the aquatic environment.     

Enzyme-induced growth of silver nanoparticles studied on single particle level

Based on their interesting properties, metal nanoparticles show the potential as an analytical tool in electronic (Burmeister et al. 2004), optical (Yguerabide and Yguerabide 1998), and catalytic applications (Liu 2006). Their characteristics depend on the composition, shape, and size of the single particles. These various properties are utilized in many different approaches such as optics, magnetics (Lang et al. 2007), and laser technology (Csaki et al. 2007). We investigated an alternative method for the synthesis of nanoparticles. In this case, an enzyme, horseradish peroxidase, induces a silver deposition and replaces a metal nanoparticle as the reaction seed. Depending on the reaction time, we could obtain particles in a range of few nanometers up to more than 250 nm. For a better understanding of the enzymatic silver deposition process, the silver particles produced by this process were analyzed by SEM, TEM, and atomic force microscopy (AFM) on a single particle level after different enhancement times. The AFM images were utilized for the characterization of particle height and volume to study the enzyme kinetics, i.e., the particle growth process. Thereby, two different phases are described: a first growth phase probably induced by the enzyme-related growth, and a second, more unspecific growth based on the metal deposition onto the silver deposits. These findings may help to use the enzyme-induced silver deposition in a quantitative manner for bioanalytical applications.     

Self-aligned nanocrystalline ZnO hexagons by facile solid-state and co-precipitation route

In this study, we report the synthesis of well-aligned nanocrystalline hexagonal zinc oxide (ZnO) nanoparticles by facile solid-state and co-precipitation method. The co-precipitation reactions were performed using aqueous and ethylene glycol (EG) medium using zinc acetate and adipic acid to obtain zinc adipate and further decomposition at 450 °C to confer nanocrystalline ZnO hexagons. XRD shows the hexagonal wurtzite structure of the ZnO. Thermal study reveals complete formation of ZnO at 430 °C in case of solid-state method, whereas in case of co-precipitation method complete formation was observed at 400 °C. Field emission scanning electron microscope shows spherical morphology for ZnO synthesized by solid-state method. The aqueous-mediated ZnO by co-precipitation method shows rod-like morphology. These rods are formed via self assembling of spherical nanoparticles, however, uniformly dispersed spherical crystallites were seen in EG-mediated ZnO. Transmission electron microscope (TEM) investigations clearly show well aligned and highly crystalline transparent and thin hexagonal ZnO. The particle size was measured using TEM and was observed to be 50–60 nm in case of solid-state method and aqueous-mediated co-precipitation method, while 25–50 nm in case of EG-mediated co-precipitation method. UV absorption spectra showed sharp absorption peaks with a blue shift for EG-mediated ZnO, which demonstrate the mono-dispersed lower particle size. The band gap of the ZnO was observed to be 3.4 eV which is higher than the bulk, implies nanocrystalline nature of the ZnO. The photoluminescence studies clearly indicate the strong violet and weak blue emission in ZnO nanoparticles which is quite unique. The process investigated may be useful to synthesize other oxide semiconductors and transition metal oxides.     

Single step surface modification of highly stable magnetic nanoparticles for purification of His-tag proteins

The aim of this study was to develop a simple, cheap, and rapid method for purification of His-tag recombinant proteins with high yields. The new immobilized metal ion affinity adsorbent containing superparamagnetic nanoparticles and hydrophilic resins are proposed here to improve the purification of His-tagged recombinant proteins. In this report, we have described the preparation of nanosized superparamagnetic nanoparticles (Fe₃O₄) which were prepared by chemical precipitation method followed by surface modification using phosphonomethyl iminodiacetic acid. The stable surface functionalized nanoparticles were further linked with Ni²⁺ for purification of 6× His-tagged proteins. The phosphonate group of the N-phosphonomethyl iminodiacetic acid ligand acts as a surface anchoring agent on magnetite nanoparticles and the remaining free –COOH groups outside for binding with Ni²⁺ ions. The nanoparticles were approximately 6–8 nm in size and were stable and had negligible non-specific binding for protein. The proteins were purified within 1 h and observed on sodium dodecyl sulfate-polyacrylamide electrophoresis gel.     

Silver-coated Si nanograss as highly sensitive surface-enhanced Raman spectroscopy substrates

We created novel surface-enhanced Raman spectroscopy (SERS) substrates by metalization (Ag) of Si nanograss prepared by a Bosch process which involves deep reactive ion etching of single crystalline silicon. No template or lithography was needed for making the Si nanograss, thus providing a simple and inexpensive method to achieve highly sensitive large-area SERS substrates. The dependence of the SERS effect on the thickness of the metal deposition and on the surface morphology and topology of the substrate prior to metal deposition was studied in order to optimize the SERS signals. We observed that the Ag-coated Si nanograss can achieve uniform SERS enhancement over large area (∼1 cm ×1 cm) with an average EF (enhancement factor) of 4.2×10⁸ for 4-mercaptophenol probe molecules. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Silver and gold nanoparticle coated membranes applied to protein dot blots

Detection and identification of low abundance biomarker proteins is frequently based on various types of membrane-based devices. Lowering of the protein detection limits is vital in commercial applications such as lateral flow assays and in Western blots widely used in proteomics. These currently suffer from insufficient detection sensitivity and low retention for small 2–5 kDa proteins. In this study, we report the deposition of two types of metal nanoparticles: gold colloids (50–95 nm diameter) and silver fractals onto a range of commonly used types of membranes including polyvinylidene fluoride (PVDF). Due to strong affinity of proteins to noble metals, such modified membranes have the potential to effectively capture trace proteins preventing their loss. The membranes modified by metal particles were characterized optically and by SEM. The membrane performance in protein dot blots was evaluated using the protein—fluorophore conjugates Deep Purple-bovine serum albumin and fluorescein—human serum albumin. We found that the metal nanoparticles increase light extinction by metals, which is balanced by increased fluorescence, so that the effective fluorescence signal is unchanged. This feature combined with the capture of proteins by the nanoparticles embedded in the membrane increases the detection limit of membrane assays.     

Newer nanoparticles in hyperthermia treatment and thermometry

Abstract  Heating tumors by nanoparticles and resistance in hypoxic tumor cells to a high temperature is emerging as an effective tool in therapeutic oncology as nanomedicine tool. The art of imaging temperature in a tumor at various locations is emerging as the selective approach of hyperthermia to monitor temperature and treat the tumor. However, thermometry and tumor cell interaction with nanoparticles may monitor and evaluate the tumor cell survival after exposure to high physiological temperatures. The application of 10–100 nanometer sized nanoparticles in tumor hyperthermia has emerged as an effective monitoring tool as magnetic resonance (MR) thermal mapping. The temperature and nanoparticle magnetic moment relationship is specific. Furthermore, there are two main issues that are unsolved as of yet. First issue is the relationship of tumor energy changes due to tumor magnetization; linear attenuation after magnetic field and X-ray exposure with tissue temperature increase. The second issue is the undefined behavior of the nanoparticle inside the tumor as diamagnetic or paramagnetic can be therapeutic and it depends on the tumor tissue temperature. In vivo imaging such as MR thermometry mapping of different hypoxic tumor locations solves these issues to some extent. The art of the nanoparticle-induced hyperthermia does have a great impact on public health as alternative therapeutic oncology. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Studies on toxicity of aluminum oxide (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) nanoparticles to microalgae species: <Emphasis Type="Italic">Scenedesmus</Emphasis> sp. and <Emphasis Type="Italic">Chlorella</Emphasis> sp.

In view of increasing commercial applications of metal oxide nanoparticles their toxicity assessment becomes important. Alumina (Al₂O₃) nanoparticles have wide range of applications in industrial as well as personal care products. In the absence of prior report on toxicological impact of alumina nanoparticles to microalgae, the principal objective of this study was to demonstrate the effect of the nanoparticles on microalgae isolated from aquatic environment (Scenedesmus sp. and Chlorella sp.). The growth inhibitory effect of alumina nanoparticles was observed for both the species (72 h EC₅₀ value, 45.4 mg/L for Chlorella sp.; 39.35 mg/L for Scenedesmus sp.). Bulk alumina also showed toxicity though to a lesser extent (72 h EC₅₀ value, 110.2 mg/L for Chlorella sp.; 100.4 mg/L for Scenedesmus sp.). A clear decrease in chlorophyll content was observed in the treated cells compared to the untreated ones, more effect being notable in the case of nanoparticles. Preliminary results based on FT-IR studies, optical and scanning electron microscopic images suggest interaction of the nanoparticles with the cell surface.     

Inhibition effects of protein-conjugated amorphous zinc sulfide nanoparticles on tumor cells growth

In this article, a facile and environmentally friendly method was applied to fabricate BSA-conjugated amorphous zinc sulfide (ZnS) nanoparticles using bovine serum albumin (BSA) as the matrix. Transmission electron microscopy analysis indicated that the stable and well-dispersed nanoparticles with the diameter of 15.9 ± 2.1 nm were successfully prepared. The energy dispersive X-ray, X-ray powder diffraction, Fourier transform infrared spectrograph, high resolution transmission electron microscope, and selected area electron diffraction measurements showed that the obtained nanoparticles had the amorphous structure and the coordination occurred between zinc sulfide surfaces and BSA in the nanoparticles. In addition, the inhibition effects of BSA-conjugated amorphous zinc sulfide nanoparticles on tumor cells growth were described in detail by cell viability analysis, optical and electron microscopy methods. The results showed that BSA-conjugated amorphous zinc sulfide nanoparticles could inhibit the metabolism and proliferation of human hepatocellular carcinoma cells, and the inhibition was dose dependent. The half maximal inhibitory concentration (IC50) was 0.36 mg/mL. Overall, this study suggested that BSA-conjugated amorphous zinc sulfide nanoparticles had the application potential as cytostatic agents and BSA in the nanoparticles could provide the modifiable site for the nanoparticles to improve their bioactivity or to endow them with the target function.