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Aluminum has gathered toxicological Attention based on relevant human exposure and its suspected hazardous potential. Nanoparticles from food supplements or Food contact materials may reach the human gastrointestinal tract.
Here, we monitored the physicochemical fate of aluminum containing nanoparticles and aluminum ions when passaging an in vitro model of the human gastrointestinal tract. Smallangle X-ray scattering (SAXS), transmission electron microscopy (TEM), ion beam microscopy (IBM), secondary ion beam mass spectrometry (TOF-SIMS), and inductively coupled plasma mass spectrometry (ICP-MS) in the singleparticle mode were employed to characterize two aluminumcontaining nanomaterials with different particle core materials (Al0, γAl2O3) and soluble AlCl3. Particle size and shape remained unchanged in saliva, whereas strong Agglomeration of both aluminum nanoparticle species was observed at low pH in gastric fluid together with an increased ion release. The levels of free aluminum ions decreased in intestinal fluid and the particles deagglomerated, thus liberating primary particles again. Dissolution of nanoparticles was limited and substantial changes of their shape and size were not detected. The amounts of particle-associated phosphorus, chlorine, potassium, and calcium increased in intestinal fluid, as compared to nanoparticles in standard dispersion.
Interestingly, nanoparticles were found in the intestinal fluid after addition of ionic aluminum. We provide a comprehensive characterization of the fate of aluminum nanoparticles in simulated gastrointestinal fluids, demonstrating that orally ingested nanoparticles probably reach the intestinal epithelium. The balance between dissolution and de novo complex formation should be considered when evaluating nanotoxicological experiments.
This paper presents the first worldwide inter-laboratory comparison of small-angle X-ray scattering (SAXS) for nanoparticle sizing. The measurands in this comparison are the mean particle radius, the width of the size distribution and the particle concentration. The investigated sample consists of dispersed silver nanoparticles, surrounded by a stabilizing polymeric shell of poly(acrylic acid). The silver cores dominate the X-ray scattering pattern, leading to the determination of their radius size distribution using (i) the generalized indirect Fourier transformation method, (ii) classical model fitting using SASfit and (iii) a Monte Carlo fitting approach using McSAS. The application of these three methods to the collected data sets from the various laboratories produces consistent mean number- and volume-weighted core radii of Rn = 2.76 (6) nm and Rv = 3.20 (4) nm, respectively. The corresponding widths of the lognormal radius distribution of the particles were σn = 0.65 (1) nm and σv = 0.71 (1) nm. The particle concentration determined using this method was 3.0 (4) g l−1 or 4.2 (7) × 10−6 mol l−1. These results are affected slightly by the choice of data evaluation procedure, but not by the instruments: the participating laboratories at synchrotron SAXS beamlines, commercial and in-house-designed instruments were all able to provide highly consistent data. This demonstrates that SAXS is a suitable method for revealing particle size distributions in the sub-20 nm region (at minimum), out of reach for most other analytical methods.
The report on the results of an in vitro digestion study of silver nanoparticles in presence and absenceof food. The particles were poly(acrylic acid) stabilized ultra-small silver nanoparticles with a radius of 3.1 nm and a relative size distribution width of 0.2. As food components oil, starch, skimmed milk powderand a mixture thereof were chosen. Aggregation of the particles was quantified with small-angle X-rayscattering in terms of log-normal radii distributions. Complete aggregation of the primary particles wasdetermined in the absence of food. In contrast, the presence of oil and starch initiates a disaggregationin the intestine. Only small aggregates of 6 nm radii and aggregation numbers of 7 were found in thepresence of milk powder. It prevents primary particles from etching in the gastric and intestinal juice.Our results indicate that the silver nanoparticles can pass the digestion process in a nanoscale form butundergo a strong and food-dependent transformation in their state of aggregation.
In the last decade the utilization of silver nanoparticles in consumer related products is strongly enhanced. Therefore, many studies focus on investigations regarding their toxicological potential. This includes investigations concerning uptake, distribution and excretion of the particles. However, little attention was paid to changes of physical and chemical properties of the particles in the human body. A major question is if the particles are size and shape persistent and can survive the digestion process. In this study we analytically monitored the changes in the size distribution of colloidal silver during an artificial digestion process with the help of small angle X-ray scattering. We synthesized poly(acrylic acid) stabilized ultra-small silver nanoparticles with a radius of 3.1 nm and a size distribution width of 20%. The artificial digestion process mimics the gastro-intestinal passage and simulates the oral, gastric and small intestinal conditions. Additionally, we used as food components oil, starch, skimmed milk powder and mixture thereof to provide a preferably realistic environment. Large aggregates of up to 56 nm were determined in the absence of food additives. In contrast, the presence of oil and starch limit the radii of aggregates to about 10 nm. Only small aggregates of 6 nm radii were found in the presence of milk powder. It prevents primary particles from etching in the intestinal juice. Our results indicate that the silver nanoparticles can pass the digestion process in a nanoscale form but undergo a strong and food-dependent transformation in their state of aggregation.
The use of silver nanoparticles in consumer related products has significantly increased over the last decade, especially due to their antimicrobial properties. Today they are used in a variety of products, which range from textiles to dietary supplements. Thus, investigations on nanoscale silver become increasingly important in many fields like biomedicine or catalysis. Unfortunately, the results of these studies are extremely diverse and do not lead to a consistent evaluation of the toxicity of silver nanoparticles. The main problem is the use of nonuniform and poorly characterized particles with broad size distributions. To overcome this problem we modified the known polyol process to synthesize ultra-small core-shell silver nanoparticles in a large scale. The particles are highly stable and show no aggregation for more than six months. Small-angle X-ray scattering analysis reveals a narrow size distribution of the silver cores with a mean radius of 3 nm and a distribution width of 0.6 nm. Dynamic light scattering provides a hydrodynamic radius of 10.0 nm and a PDI of 0.09. The stabilizing ligand PAA can be easily exchanged by biomolecules to modify the surface functionality. Replacements of PAA with glutathione and bovine serum albumin have been successfully performed. To demonstrate the broad applicability of our particles we performed catalysis experiments with the reduction of 4-nitrophenol as model reaction. The PAA-stabilized particles show a catalytic activity of (436 ± 24) L g-1 s-1, which is the highest reported in literature for silver nanoparticles. In contrast, GSH and BSA passivate the surface substantially resulting in lower catalytic activities.
Tracking silver nanoparticles: ultra-small silver refunctionalizable with fluorescent biopolymers
(2016)
We report on the synthesis of ultra-small silver nanoparticles and their quantitative characterization by small-angle X-ray scattering. The size distribution was derived by utilizing a Monte-Carlo data evaluation procedure reported by Pauw et al. Mean volume-weighted sizes are 3 nm with a size distribution width of 18 %. The particles should be used as reference materials for comparison of the result of different analytical methods among which are field-flow fractionation (FFF), dynamic light scattering (DLS), nanoparticle tracking analysis (NTA) and electron microscopy (EM). In addition further use of the particles is foreseen for comparison of studies on the toxicology of nanoparticles. Therefore the silver nanoparticles are transfunctionalized with fluorescent marked albumin (BSA-FITC) and also thoroughly characterized. With this it is possible to track silver nanoparticles and their behavior in interaction with cells.
The use of silver nanoparticles in consumer related products has significantly increased over the last decade, especially due to their antimicrobial properties. Today they are used in a variety of products, which range from textiles over children toys and dietary supplements. Therefore, research on silver in a nanoscale form becomes increasingly important for a high amount of studies. Unfortunately the results of these studies are extremely diverse and do not lead to a consistent evaluation of the toxicity of silver nanoparticles. The central problem lies in the utilization of a wide range of silver nanoparticles, which show a broad size distribution. To overcome this problem we synthesized ultra-small core-shell silver nanoparticles by an up-scaled modification of the polyol process. The particles are highly stable and show no aggregation for more than six months. Small-angle X-ray scattering (SAXS) analysis reveal a narrow size distribution of the silver cores with a mean radius of RC = 3.0 nm and a distribution width of 0.6 nm. Dynamic light scattering (DLS) provides a hydrodynamic radius of RH = 10.0 nm and a PDI of 0.09. The surface of the particles is covered with poly(acrylic acid) (PAA) forming a shell with a thickness of 7.0 nm, which provides colloidal stability lasting for more than six months at ambient conditions. It is foreseen to use these thoroughly characterized particles as reference material to compare the catalytic and biological properties of functionalized silver nanoparticles. The stabilizing ligand PAA can be easily exchanged by biomolecules to modify the surface functionality. Replacements of PAA with glutathione (GSH) and bovine serum albumin (BSA) have been performed as examples. We demonstrate that the particles effectively catalyze the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride. With PAA as stabilizer, the catalytic activity of (436 ± 24) L g-1 s-1 is the highest reported in literature for silver nanoparticles. GSH and BSA passivate the surface substantially resulting in lower catalytic activities of (77.6 ± 0.9) L g-1 s-1 and (3.47 ± 0.50) L g-1 s-1, respectively. The ultra-small particles were already used in the Nano Define project. Due to their small size it is possible to investigate the detection limits of different analytical techniques like electron microcopy, field flow fractionation or single particle tracking. In this project they serve as the calibration standard with the smallest radius.
In the last decade the utilization of silver nanoparticles in consumer related products is enhanced. Therefore, many studies focus on investigations regarding their toxicological potential. This includes investigations concerning uptake, distribution and excretion of the particles. So far, little attention was paid to changes of physical and chemical properties in the human body. During processes like digestion, the question arises whether they can pass this barrier in a nanoscale form. In this study we analytically monitored the changes in the size distribution of colloidal silver during an artificial digestion process with the help of small angle x-ray scattering (SAXS). Therefore, we synthesized polyacrylic acid stabilized ultra-small silver nanoparticles with a radius of 3 nm and a size distribution width of 18%. The artificial digestion process mimics the gastro-intestinal passage and simulates the oral, gastric and small intestinal conditions. Additionally, food components like oil, starch, glucose and skimmed milk powder are used to provide a preferably realistic environment.
In absence of any food components the low pH initiates aggregation of the particles in the stomach. However, the particles unexpectedly stabilize in a defined cluster form with a mean radius of 12 nm. By the use of the food components oil and starch we observed that the particles are dispersed again. Now we found a bimodal size distribution of primary particles and aggregates. In contrast to that, with skimmed milk powder only a slight aggregation occurs in the stomach. In the gastric tract the particle distribution is stabilized at a mean volume weighted radius of 5 nm. Hence, skimmed milk powder acts as a colloidal stabilizer. For comparison we also used silver nitrate as a control substance. Surprisingly, we observed a formation of nanoparticles already in the saliva. During the digestion process the distribution narrows and finally in the intestine it shows a stable distribution with a mean volume weighted radius of 3 nm and a small fraction of aggregates. These results indicate that the silver nanoparticles can pass the digestion process in a nanoscale form but undergo a transformation in the size distribution. However, even from pure silver nitrate nanoparticle formation can be observed. This sketches a complex mechanism in which not only food components but also silver ions cause changes in nanoparticle size and aggregation.