Kinetic stability of hematite nanoparticles: the effect of particle sizes

Nanoparticles are ubiquitous in environment and are potentially important in many environmental processes such as sorption, coprecipitation, redox reactions, and dissolution. To investigate particle size effects on nanoparticle aggregation and stability, this study tested aggregation behavior of 12(±2), 32(±3), and 65(±3) nm (hydrated radius) hematite particles under environmental relevant pH and ionic strength conditions. The results showed that at the same ionic strength and pH conditions, different particle sizes show different tendency to aggregate. At the same ionic strength, aggregation rates are higher for smaller particles. The critical coagulation concentration also depends on particle size, and decreases as particle size decreases. As the particle size decreases, fast aggregation shifted to lower pH. This may be related to a dependence of PZC on particle size originating from change of structure and surface energy characteristics as particle size decreases. Under the same conditions, aggregation occurs faster as particle concentration increases. Even though the nanoparticles of different sizes show different response to the same pH and ionic strength, DLVO theory can be used to qualitatively understand hematite nanoparticle aggregation behavior.     

A review of the antibacterial effects of silver nanomaterials and potential implications for human health and the environment

Here, we present a review of the antibacterial effects of silver nanomaterials, including proposed antibacterial mechanisms and possible toxicity to higher organisms. For purpose of this review, silver nanomaterials include silver nanoparticles, stabilized silver salts, silver–dendrimer, polymer and metal oxide composites, and silver-impregnated zeolite and activated carbon materials. While there is some evidence that silver nanoparticles can directly damage bacteria cell membranes, silver nanomaterials appear to exert bacteriocidal activity predominantly through release of silver ions followed (individually or in combination) by increased membrane permeability, loss of the proton motive force, inducing de-energization of the cells and efflux of phosphate, leakage of cellular content, and disruption DNA replication. Eukaryotic cells could be similarly impacted by most of these mechanisms and, indeed, a small but growing body of literature supports this concern. Most antimicrobial studies are performed in simple aquatic media or cell culture media without proper characterization of silver nanomaterial stability (aggregation, dissolution, and re-precipitation). Silver nanoparticle stability is governed by particle size, shape, and capping agents as well as solution pH, ionic strength, specific ions and ligands, and organic macromolecules—all of which influence silver nanoparticle stability and bioavailability. Although none of the studies reviewed definitively proved any immediate impacts to human health or the environment by a silver nanomaterial containing product, the entirety of the science reviewed suggests some caution and further research are warranted given the already widespread and rapidly growing use of silver nanomaterials.     

Stability of polyvinyl alcohol-coated biochar nanoparticles in brine

This paper reports on the dispersion stability of 150 nm polyvinyl alcohol coated biochar nanoparticles in brine water. Biochar is a renewable, carbon based material that is of significant interest for enhanced oil recovery operations primarily due to its wide ranging surface properties, low cost of synthesis, and low environmental toxicity. Nanoparticles used as stabilizing agents for foams (and emulsions) or in nanofluids have emerged as potential alternatives to surfactants for subsurface applications due to their improved stability at reservoir conditions. If, however, the particles are not properly designed, they are susceptible to aggregation because of the high salinity brines typical of oil and gas reservoirs. Attachment of polymers to the nanoparticle surface, through covalent bonds, provides steric stabilization, and is a necessary step. Our results show that as the graft density of polyvinyl alcohol increases, so too does the stability of nanoparticles in brine solutions. A maximum of 34 wt% of 50,000 Da polyvinyl alcohol was grafted to the particle surface, and the size of the particles was reduced from ~3500 nm (no coating) to 350 nm in brine. After 24 h, the particles had a size of ~500 nm, and after 48 h completely aggregated. 100,000 Da PVA coated at 24 wt% on the biochar particles were stable in brine for over 1 month with no change in mean particle size of ~330 nm.     

纳米氧化锌的过饱和控制生长与大小分布控制.

"在非水介质中合成了纳米氧化锌,测定了纳米氧化锌的紫外吸收光谱,并用有效质量模型计算了粒子大小,开发并命名了一种称之为纳米粒子过饱和控制生长的技术,该技术涉及将小的纳米粒子悬浊液加入到大的粒子悬浊液中,结果因为不同大小粒子间的溶解度差异小的粒子将全部溶解,大的粒子将整体长大,大粒子悬浊液的粒子数将保持不变,大粒子的生长速度显著比Ostwald老化的高．该技术最显著的特征是只要最初两悬浊液粒子大小的差异足够大,分布不是太宽,则粒子大小的分布将会因为粒子如此长大而变窄．"     

Experimental study of nanoparticles penetration through commercial filter media

In this study, nanoparticle penetration was measured with a wide range of filter media using silver nanoparticles from 3 nm to 20 nm at three different face velocities in order to define nanoparticle filtration characteristics of commercial fibrous filter media. The silver particles were generated by heating a pure silver powder source via an electric furnace with a temperature of 870°C, which was found to be the optimal temperature for generating an adequate amount of silver nanoparticles for the size range specified above. After size classification using a nano-DMA, the particle counts were measured by an Ultrafine Condensation Particle Counter (UCPC) both upstream and downstream of the test filter to determine the nanoparticle penetration for each specific particle size. Particle sampling time continued long enough to detect more than 10⁵ counts at the upstream and 10 counts at the downstream sampling point so that 99.99% efficiency can be detected with the high efficiency filter. The results show a very high uniformity with small error bars for all filter media tested in this study. The particle penetration decreases continuously down to 3 nm as expected from the classical filtration theory, and together with a companion modeling paper by␣Wang et al. in this same issue, we found no significant evidence of nanoparticle thermal rebound down to 3 nm.     

Phytosynthesis of Silver Nanoparticles Using Andrographis paniculata Leaf Extract and Evaluation of Their Antibacterial Activities

Use of nanotechnology in biological systems by the synthesis of metallic nanoparticles is a burning area of research in recent times. In the present investigation, aqueous extract of Andrographis paniculata was used to produce silver nanoparticles by reduction of silver nitrate. It was noted that the synthesizing process was quite rapid and silver nanoparticles form within minutes of silver ions coming in contact with plant extract. UV-Vis spectrum of the aqueous medium containing silver ions indicated a peak at 432 nm corresponding to the plasmon absorbance of the silver nanoparticles. Fourier transform infrared spectroscopic analysis of the silver nanoparticles showed the presence of proteins that might be acting as capping agents around the nanoparticles. From scanning electron microscopy analysis, the size of the silver nanoparticles was measured and it was found that the average size was between 40 and 60 nm. Furthermore, the antibacterial activity of synthesized silver nanoparticles exhibited effective inhibition zones against seven bacterial strains tested. Among the bacteria tested Pseudomonas aeruginosa was found to be most susceptible to the silver nanoparticles. Phytochemical screening of the plant extract indicated the presence of alkaloids, flavonoids, amino acids, saponins, tannins, and terpenoids.     

Corrosion processes of triangular silver nanoparticles compared to bulk silver

Excessive corrosion of silver nanoparticles is a significant impediment to their use in a variety of potential applications in the biosensing, plasmonic and antimicrobial fields. Here we examine the environmental degradation of triangular silver nanoparticles (AgNP) in laboratory air. In the early stages of corrosion, transmission electron microscopy shows that dissolution of the single-crystal, triangular, AgNP (side lengths 50–120 nm) is observed with the accompanying formation of smaller, polycrystalline Ag particles nearby. The new particles are then observed to corrode to Ag₂S and after 21 days nearly full corrosion has occurred, but some with minor Ag inclusions remaining. In contrast, a bulk Ag sheet, studied in cross section, showed an adherent corrosion layer of only around 20–50 nm in thickness after over a decade of being exposed to ambient air. The results have implications for antibacterial properties and ecotoxicology of AgNP during corrosion as the dissolution and reformation of Ag particles during corrosion will likely be accompanied by the release of Ag⁺ ions.     

SERS characterization of metallic silver nanoparticle self‐assembly within thin films

Clusters of silver nanoparticles are generated by the thermally initiated reduction of silver carboxylates (long‐chain fatty acids) in the thin polymer films. The size, shape, and aggregation of these nanoparticles are affected by the reduction reaction in the presence of capping agents. In order to understand the mechanism(s) controlling the silver structure formation, it is essential to understand the surface coordination chemistry occurring during this process. We now report the first application of surface‐enhanced Raman spectroscopy (SERS) to directly characterize adsorbates on the surfaces of silver nanoparticles within a thin film imaging construction containing multiple components. In addition, SERS investigation of model silver substrates was used to confirm the identify of specific adsorbates of silver complexes. This is a powerful tool for revealing the chemistry involved with the control of silver nanoparticle aggregation during thermally induced metallic silver formation within thin films. Both the catechol‐reducing agent and the phthalazinone (PAZ) particle aggregation agent are observed on the metallic silver surface at the initial particle formation and during its crystal growth. However, careful attention to excitation wavelength is required in order to observe all the surface species. PAZ appears to be more effective at stabilizing individual silver particles than other aggregation agents investigated. An understanding of the roles of the aggregation/reducing agents in the growth and aggregation of silver nanoparticles is important for preparing different types of silver particles for specific applications including silver‐based thermal imaging systems. Copyright © 2008 John Wiley & Sons, Ltd.     

Transition metal doping of amorphous silica particles

Amorphous, homogeneously doped particles with 1–10 atomic percent (at%) nickel or zinc, smaller than 100 nm, were synthesized. Additionally, 20 at% nickel and zinc-doped silica particles were synthesized, although the particle size was > 300 nm. The coordination state of the metal in solution did not change with the ammonia or water concentrations used. Particle size was found to decrease with both increasing water and ammonia hydroxide concentrations. The NH₄OH concentrations of 4.5 and 6.5 M used allowed the formation of ammine–transition metal complexes and the zeta potential to remain in a stable range, allowing for spherical, nearly monodisperse particle formation at high metal dopant concentrations.     

Fabrication and electrochemical property modification of mixed matrix heterogeneous cation exchange membranes filled with Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/PAA core-shell nanoparticles

In the current research, iron oxide nanoparticles were functionalized by acrylic acid polymerization. The Fe₃O₄/PAA core-shell nanoparticles were utilized for the modification of cation exchange membranes. Ion exchange membranes were prepared by solution casting technique using cation exchange resin powder as functional group agent and tetrahydrofuran as solvent. FTIR analysis proved the formation of PAA on nanoparticles. The SOM images also showed uniform particle distribution for the prepared membrane relatively. The membrane water content was declined from 30 to 17 % by increase of nanoparticle content ratio in membrane matrix. The contact angle measurements showed that membrane surface hydrophilicity was improved by utilizing of nanoparticles in the membrane matrix. The membrane potential, permselectivity, and transport number were improved initially by increase of nanoparticle concentration in the casting solution and then began to decrease by more additive concentration. Membrane ionic flux and permeability were enhanced initially by increase of nanoparticle loading ratio up to 0.5 %wt in membrane matrix and then showed decreasing trend by more increase of nanoparticle concentration from 0.5 to 4 %wt. Membrane areal electrical resistance was decreased sharply by utilization of nanoparticles up to 0.5 %wt in membrane matrix then began to increase by more additive concentration. The prepared membranes exhibited superior selectivity and low ionic flux at neutral condition compared to other acidic and alkaline environments.     

Self-assembled silver nanoparticles: correlation between structural and surface plasmon resonance properties

We report a facile method for controllable fabrication of high-density silver nanoparticle films with a widely adjustable surface plasmon resonance (SPR) frequency, based on the gas phase cluster beam deposition. On the one hand, we can control the particle size by depositing clusters on silica substrate. Light extinction spectra of the self-assembled Ag nanoparticles with various particle sizes are characterized and show two SPRs, in which a SPR exhibits a redshift from less 400 nm to more than 570 nm with an increase in the particle size, whereas the other shows a slight position shifting. On the other hand, the inter-particle distance of the self-assembled Ag nanoparticles can also be controlled by depositing clusters on silica glass coated with Formvar film, and the SPR wavelength shows a redshift from <400 nm to more than 560 nm, which can be attributed to the increase of the fraction of closely spaced nanoparticle pairs that are near-field coupled with the deposition mass. The size and coverage-dependent SPR properties are also compared with the results from the discrete dipole approximation calculations. The present method of tailoring metallic microstructures could find important applications in plasmonics.     

Silver Nanoparticle Based Analysis of Aminoglycosides

Colorimetric silver nanoparticle sensor was developed for determination of aminoglycosides in milk. Silver nanoparticles were synthesized by using sodium borohydride as reducing agent and sodium dodecyl sulfate as stabilizer. Yellow color of silver turned into orange and red in proportion to the concentrations of analytes. Quantitative analyses were performed by using decrease in absorbance of silver nanoparticles at 394 nm. Linear ranges were 20–60 ng mL^?1, 23–60 ng mL^?1, and 60–100 ng mL^?1 for gentamicin, tobramycin, and amikacin, respectively. The method was optimized in terms of pH, ionic strength, and time. This simple and validated method was applied to milk samples and pharmaceutical preparations.     

Silver release from nanocomposite Ag/alginate hydrogels in the presence of chloride ions: experimental results and mathematical modeling

A stepwise experimental and mathematical modeling approach was used to assess silver release from nanocomposite Ag/alginate microbeads in wet and dried forms into water and into normal saline solution chosen as a simplified model for certain biological fluids (e.g., blood plasma, wound exudates, sweat, etc). Three phenomena were connected and mathematically described: diffusion of silver nanoparticles (AgNPs) within the alginate hydrogel, AgNP oxidation/dissolution and reaction with chloride ions, and diffusion of the resultant silver-chloride species. Mathematical modeling results agreed well with the experimental data with the AgNP diffusion coefficient estimated as 1.3 × 10^?18 m² s^?1, while the first-order kinetic rate constant of AgNP oxidation/dissolution and diffusivity of silver-chloride species were shown to be inversely related. In specific, rapid rehydration and swelling of dry Ag/alginate microbeads induced fast AgNP oxidation/dissolution reaction with Cl^? and AgCl precipitation within the microbeads with the lowest diffusivity of silver-chloride species compared to wet microbeads in normal saline. The proposed mathematical model provided an insight into the phenomena related to silver release from nanocomposite Ca-alginate hydrogels relevant for use of antimicrobial devices and established, at the same time, a basis for further in-depth studies of AgNP interactions in hydrogels in the presence of chloride ions.     

Targeting EGFR-overexpressed A431 cells with EGF-labeled silica-coated magnetic nanoparticles

Electrode catalysts composed of carbon-supported PtRu nanoparticles (PtRu/C) for use as a direct methanol fuel cell anode were synthesized by the reduction of precursor ions in an aqueous solution via irradiation with a high-energy electron beam. The effect of pH control in the precursor solution on the PtRu mixing state and the methanol oxidation activity was studied in order to enhance the catalytic activity for methanol oxidation. The PtRu/C structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray fluorescence spectrometry, and X-ray diffraction and X-ray absorption fine structure techniques. The methanol oxidation activity was evaluated by linear sweep voltammetry. The initial pH of the precursor solution has little influence on the average grain size for the metal particles (approximately 3.5 nm) on the carbon particle supports, but the dispersibility of the metal particles, PtRu mixing state, and methanol oxidation activity differed. The maintenance of a low pH in the precursor solution gave the best dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles, whereas, a high pH gave the best PtRu mixing state and the highest oxidation current although a low dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles was obtained. The PtRu mixing state strongly correlated with the methanol oxidation current. In addition, a high pH was more effective for PtRu mixing when using an electron beam irradiation reduction method, because the complexation reaction of the chelating agents was improved, which resulted in an enhancement of the catalytic activity for methanol oxidation.     

Synthesis of magnetic nanoparticles: effects of polyelectrolyte concentration and pH

This study refers to the effect of sodium polyacrylate concentration (1 to 5 mass %) and pH (10 to 12) on the synthesis of magnetic nanoparticles (magnetite?Cmaghemite) and their characterization by Mössbauer spectroscopy. The magnetic particles were obtained by coprecipitation method using iron chloride (II) and iron chloride (III) as precursor reagents and sodium polyacrylate as stabilizing agent. All samples showed Mössbauer broad resonance lines in typical doublet and sextets patterns of magnetite or maghemite with corresponding wide particle size distributions. The stability of magnetic particles was carried out by measuring particle sizes with dynamic light scattering (DLS). The z-average values for magnetic particles were in the range 24 to 590 nm and no significant change in size was observed on aging by leaving this material in air for 20 days. X-ray diffraction patterns showed characteristic peaks of the spinel structure and have an increase in their broadening as the pH decreases, effect that is dominated by the decrease in crystallite sizes. The nanoparticles showed to be magnetic at pH 12 and at room temperature.     

Preparation of magnetic nanoparticles by pulsed plasma chemical vapor synthesis

FePt nanoparticle is expected as a candidate for the magnetic material of the high density recording media. We attempted to synthesize FePt alloy nanoparticles using 13.56 MHz glow discharge plasma with the pulse operation of a square-wave on/off cycle of plasma discharge to control the size of nanoparticles. Vapors of metal organics, Biscyclopentadienyl iron (ferrocene) for Fe and (Methylcyclopentadienyl) trimethyl platinum for Pt, were introduced into the capacitively coupled flow-through plasma chamber, which consisted of shower head RF electrode and grounded mesh electrode. Synthesis experiments were conducted at room temperature under the conditions of pressure 0.27 Pa, source gas concentration 0.005 Pa, gas residence time 0.5 s and plasma powers 60 watts. Pulse width for plasma duration was chosen from 0.5 to 30 s and plasma off period was 4 s to each pulse operation. Visual observations during the particle growth showed plasma emission in the bulk region was increased with the particle growth. These were theoretically explained by using the model for both transient particle charging in the plasma and single particle behavior in the stationary plasma as well as assuming the similarity between the negative charged particle and negative gas containing plasma. Synthesized nanoparticles were directly collected onto TEM grid, which was placed just below the grounded mesh electrode in the plasma reactor downstream. TEM pictures showed two kinds of particles in size, one of which was nanometer size and isolated with crystal structures and the other appeared agglomerate of nanometer size particles. The size of agglomerated particle was controlled in the 10–120 nm range by varying the plasma-on time from 0.5 to 30 s, although the nanometer size particles did not change. The composition of FePt alloy particles could be altered by adjusting the source gas feed ratio. Also magnetization of FePt nanoparticles was measured by use of SQUID (superconducting quantum interference device) magnetometry measurements. As-synthesized FePt nanoparticles did not exhibit loop-shape characteristic, which indicated superpamagnetic property. Annealed nanoparticles with the composition of Fe₅₈Pt₄₂ at 650°C in atmospheric hydrogen showed clear hysterisis loop with the coercivity as large as 10 KOe.     

Workplace air measurements and likelihood of exposure to manufactured nano-objects,agglomerates, and aggregates

Workplace exposure to nanoparticles from gas metal arc welding (GMAW) process in an automobile manufacturing factory was investigated using a combination of multiple metrics and a comparison with background particles. The number concentration (NC), lung-deposited surface area concentration (SAC), estimated SAC and mass concentration (MC) of nanoparticles produced from the GMAW process were significantly higher than those of background particles before welding (P < 0.01). A bimodal size distribution by mass for welding particles with two peak values (i.e., 10,000–18,000 and 560–320 nm) and a unimodal size distribution by number with 190.7-nm mode size or 154.9-nm geometric size were observed. Nanoparticles by number comprised 60.7 % of particles, whereas nanoparticles by mass only accounted for 18.2 % of the total particles. The morphology of welding particles was dominated by the formation of chain-like agglomerates of primary particles. The metal composition of these welding particles consisted primarily of Fe, Mn, and Zn. The size distribution, morphology, and elemental compositions of welding particles were significantly different from background particles. Working activities, sampling distances from the source, air velocity, engineering control measures, and background particles in working places had significant influences on concentrations of airborne nanoparticle. In addition, SAC showed a high correlation with NC and a relatively low correlation with MC. These findings indicate that the GMAW process is able to generate significant levels of nanoparticles. It is recommended that a combination of multiple metrics is measured as part of a well-designed sampling strategy for airborne nanoparticles. Key exposure factors, such as particle agglomeration/aggregation, background particles, working activities, temporal and spatial distributions of the particles, air velocity, engineering control measures, should be investigated when measuring workplace exposure to nanoparticles.     

Fabrication and characterization of iron oxide nanoparticles filled polypyrrole nanocomposites

The effect of iron oxide nanoparticle addition on the physicochemical properties of the polypyrrole (PPy) was investigated. In the presence of iron oxide nanoparticles, PPy was observed in the form of discrete nanoparticles, not the usual network structure. PPy showed crystalline structure in the nanocomposites and pure PPy formed without iron oxide nanoparticles. PPy exhibited amorphous structure and nanoparticles were completely etched away in the nanocomposites formed with mechanical stirring over a 7-h reaction. The thermal stability of the PPy in the nanocomposites was enhanced under the thermo-gravimetric analysis (TGA). The electrical conductivity of the nanocomposites increased greatly upon the initial addition (20 wt%) of iron oxide nanoparticles. However, a higher nanoparticle loading (50 wt%) decreased the conductivity as a result of the dominance of the insulating iron oxide nanoparticles. Standard four-probe measurements indicated a three-dimensional variable-range-hopping conductivity mechanism. The magnetic properties of the fabricated nanocomposites were dependent on the particle loading. Ultrasonic stirring was observed to have a favorable effect on the protection of iron oxide nanoparticles from dissolution in acid. A tight polymer structure surrounds the magnetic nanoparticles, as compared to a complete loss of the magnetic iron oxide nanoparticles during conventional mechanical stirring for the micron-sized iron oxide particles filled PPy composite fabrication.     

Diversity of TiO<Subscript>2</Subscript> nanopowders’ characteristics relevant to toxicity testing

In this study, the physicochemical properties of several commercial ultrafine TiO₂ powders and their behaviour in the as-received form and colloidal suspensions were analysed. Besides the particle size, the morphology and agglomeration state of the dry powders, dispersibility, ζ-potential and sedimentation in water and in phosphate-buffered saline (PBS) were studied. Also, leaching of ions from the powders during ageing in physiological solution and the ability of the photoactivated powders to decompose organic substances were evaluated. The examined TiO₂ powders revealed diversified characteristics when dispersed in water. In general, while in dry conditions the particle size appeared in the nano-range (down to 32 nm), the particles were agglomerated in aqueous suspensions at pH ~7 and only a minor amount showed dimensions below 200 nm, but none below 100 nm. The inherent pH of the 3 % suspensions varies from 3.7 to 7.5 and the surface charge at these pH values varied from highly positive to highly negative values. In PBS, the surface charge is negative and relatively low for all the samples, which resulted in agglomeration. Five out of six powders exhibited significant photocatalytic activity when exposed to UV irradiation. This also includes one cosmetic-grade powder. Furthermore, during the immersion in aqueous media at physiological temperature, the powders released foreign ions, which might also contribute to the results of cytotoxicity tests. The results revealed the major role of the particle surface charge and its impact on particle dispersion or agglomeration. Due to the high ionic strength in the liquids relevant for cell-surface interaction tests, for all the examined titania powders the nanoparticulate character was lost. However, the presence of impurities and photocatalysis might further contribute to the results of cytotoxicity tests.