An on-line measurement and control system for submerged arc spray synthesis of TiO2 nanoparticles

This article presents the development of an on-line measurement and control system for process characterization and optimization of the nanoparticle manufacturing process, called the submerged arc-spray nanoparticle synthesis system (SANSS). To achieve optimized control of particle uniformity, this research investigates the feasibility of employing optical fiber probe and the dynamic light scattering (DLS) technique to monitor and control particle sizes. According to the theory of DLS, an on-line nanoparticle sampling and measurement system was developed and integrated with the SANSS as an important step to verify the measurement performance of the proposed method. To examine the measurement accuracy of the developed system, calibrated polystyrene latex particles with known accurate sizes were employed to verify the particle sizing accuracy of the proposed system. The data conformity between the measurement results of TiO, nanoparticles obtained by various methods, including TEM, a calibrated commercial particle sizing system and the on-line measurement system, has indicated that the developed method was feasible and effective.     

Comparative Nanoparticle Size Characterization of EEW Alumina Using Various Measurement Techniques

Modern material science is paying more attention on the development of nanomaterials for superior properties in various fields of applications like mechanical, thermal, electronic, bio-medical etc. For such applications, determination of nanoparticle sizes along with their distribution is important for attaining the desired properties. Particle sizes along with the crystallite sizes of oxides, non-oxides and metallic nanopowders produced by different processes can be determined by different techniques which includes x-ray diffraction/neutron diffraction (XRD/ND), transmission electron microscopy/field emission scanning electron microscopy (TEM/FESEM), Brunauer-Emmett-Teller (BET) surface area method, small angle neutron scattering (SNAS), dynamic light scattering (DLS), static light scattering (SLS), etc. For average nano-metric particle size determination, DLS is the most frequently used technique that gives a distribution that approximates the exact binomial distribution of large numbers of nanoparticulates with varying particle size under investigation (Gaussian distribution). However, the other techniques mainly give either localized distribution of the particles under observation or the distribution derived from type II isotherm. In this investigation, nano-alumina powder produced by the electrical explosion of wire technique (EEW) is used for comparative evaluation of particle size analysis by DLS measurement technique for nanoparticles vis-à-vis to other techniques like XRD (for crystallite size), FESEM, BET, and TEM. The superiority of the DLS technique has been discussed in details with respect to the unique features of its Gaussian distribution nature.     

Laser Heating Tunability by Off‐Resonant Irradiation of Gold Nanoparticles

Temperature changes in the vicinity of a single absorptive nanostructure caused by local heating have strong implications in technologies such as integrated electronics or biomedicine. Herein, the temperature changes in the vicinity of a single optically trapped spherical Au nanoparticle encapsulated in a thermo‐responsive poly(N‐isopropylacrylamide) shell (Au@pNIPAM) are studied in detail. Individual beads are trapped in a counter‐propagating optical tweezers setup at various laser powers, which allows the overall particle size to be tuned through the phase transition of the thermo‐responsive shell. The experimentally obtained sizes measured at different irradiation powers are compared with average size values obtained by dynamic light scattering (DLS) from an ensemble of beads at different temperatures. The size range and the tendency to shrink upon increasing the laser power in the optical trap or by increasing the temperature for DLS agree with reasonable accuracy for both approaches. Discrepancies are evaluated by means of simple models accounting for variations in the thermal conductivity of the polymer, the viscosity of the aqueous solution and the absorption cross section of the coated Au nanoparticle. These results show that these parameters must be taken into account when considering local laser heating experiments in aqueous solution at the nanoscale. Analysis of the stability of the Au@pNIPAM particles in the trap is also theoretically carried out for different particle sizes.     

Large-scale, reliable and robust SERS-active nanowire substrates prepared using porous alumina templates

nanowire arrays for surface-enhanced Raman scattering applications. These nanowire films were synthesized via electrodeposition using porous alumina templates of varying order, thickness and pore diameters. Mechanical polishing has been shown to be a very effective method to prepare nanowire arrays with monodisperse length over comprehensively large dimensions. On the other hand, a convenient synthesis route has been suggested that allows the formation of nanoparticle rrays using very thin and/or large area porous alumina films. It is reckoned that even films with the smallest obtainable pore sizes can be utilized to prepare large area, fine nanoparticle arrays. Such arrays may also find use in other areas, such as solar cells and electrochemistry. Preliminary Raman experiments indicated that the nanowire/nanoparticle arrays are indeed surface-enhanced Raman scattering-active. Finally, the potentials offered by the reported processing methods for fabricating substrates with predictable and high Raman amplifications are discussed.     

Intermethod comparison of the particle size distributions of colloidal silica nanoparticles

There can be a large variation in the measured diameter of nanoparticles depending on which method is used. In this work, we have strived to accurately determine the mean particle diameter of 30–40 nm colloidal silica particles by using six different techniques. A quantitative agreement between the particle size distributions was obtained by scanning electron microscopy (SEM), and electrospray-scanning mobility particle sizer (ES-SMPS). However, transmission electron microscopy gave a distribution shifted to smaller sizes. After confirming that the magnification calibration was consistent, this was attributed to sample preparation artifacts. The hydrodynamic diameter, d _h , was determined by dynamic light scattering (DLS) both in batch mode, and hyphenated with sedimentation field flow fractionation. Surprisingly the d _h were smaller than the SEM, and ES-SMPS diameters. A plausible explanation for the smaller sizes found with DLS is that a permeable gel layer forms on the particle surface. Results from nanoparticle tracking analysis were strongly biased towards larger diameters, most likely because the silica particles provide low refractive index contrast. Calculations confirmed that the sensitivity is, depending on the shape of the laser beam, strongly size dependent for particles with diameters close to the visualization limit.     

Validation of dynamic light scattering and centrifugal liquid sedimentation methods for nanoparticle characterisation

A variety of techniques exists to analyse the size and size distribution of nanoparticles in a suspension. However, these nanoparticle characterisation methods have been rarely fully validated and appropriate reference materials with properly assigned SI traceable values are not easily found. This paper presents results of in-house validation studies of Dynamic Light Scattering (DLS) and Centrifugal Liquid Sedimentation (CLS) methods. During these studies, a silica nanoparticle reference material was tested under repeatability and intermediate precision conditions. The trueness of the DLS and CLS methods was investigated by measuring gold and polystyrene nanoparticle reference materials. Furthermore, for each method, an uncertainty budget has been established. Both method validation and estimation of reliable measurement uncertainties are prerequisites for the certification of new nanoparticle reference materials.     

3D Printing of Viscoelastic Suspensions via Digital Light Synthesis for Tough Nanoparticle–Elastomer Composites

The rheological parameters required to print viscoelastic nanoparticle suspensions toward tough elastomers via Digital Light Synthesis (DLS) (an inverted projection stereolithography system) are reported. With a model material of functionalized silica nanoparticles suspended in a poly(dimethylsiloxane) matrix, the rheological-parameters-guided DLS can print structures seven times tougher than those formed from the neat polymers. The large yield stress and high viscosity associated with these high concentration nanoparticle suspensions, however, may prevent pressure-driven flow, a mechanism essential to stereolithography-based printing. Thus, to better predict and evaluate the printability of high concentration nanoparticle suspensions, the boundary of rheological properties compatible with DLS is defined using a non-dimensional Peclet number (Pe). Based on the proposed analysis of rheological parameters, the border of printability at standard temperature and pressure (STP) is established by resin with a silica nanoparticle mass fraction (ϕ_silica) of 0.15. Above this concentration, nanoparticle suspensions have Pe > 1 and are not printable. Beyond STP, the printability can be further extended to ϕ_silica = 0.20 via a heating module with lower shear rate to reduce the Pe < 1. The printed rubber possesses even higher toughness (Γ ≈ 155 kJ m⁻³), which is 40% higher over that of ϕ_silica = 0.15.     

High sensitivity luminescence nanoparticle assay for the detection of protein aggregation

Nanoparticle assay utilizing time-resolved luminescence resonance energy transfer (TR-LRET) was developed for the detection of protein aggregation. This mix-and-measure nanoparticle assay is based on the competitive adsorption of the sample and the acceptor-labeled protein to donor europium(III) polystyrene particles. The protein aggregation was detected with the developed TR-LRET nanoparticle assay, UV240 absorbance and dynamic light scattering (DLS). All methods well equally detected the aggregation and aggregates, whose size ranged from single protein to more than 1000 nm aggregates. The developed method allowed the aggregation detection of the entire size range at more than 10,000 times lower concentration, 30 μg/L, compared to UV240 and DLS. The simple-to-use and sensitive nanoparticle assay with existing microtiter plate luminometric instrumentation can find use as a routine tool for protein aggregation studies in biochemical laboratories and for quality assessment of protein products in industry.     

Nanoparticle Assemblies on Nanoinjection-Molded Polymer Templates

A mass-producible method for fabricating nanoparticle assemblies using nanoinjection-molded polymer templates with deposition and selective removal has been developed and characterized in this work. Results are demonstrated for assembly of multiple nanoparticle sizes and types in 1-D and 2-D formats over large areas. Template dimensions such as width and depth are used to control the assembled structures, including the quantity and type of nanoparticles in the assembly. This method offers a high-throughput, low-cost approach to nanoscale assembly for applications in optical, electronic, and biomedical devices.      

Green Synthesis of Silver Nanoparticles Using an Otherwise Worthless Weed Mimosa (Mimosa pudica): Feasibility and Process Development Toward Shape/Size Control

A bioinspired method of silver nanoparticle (AgNP) synthesis using the highly invasive terrestrial weed mimosa (Mimosa pudica) is presented. An aqueous extract of the leaves of the weed that served as a reducing and stabiliaing agent was employed in various proportions with Ag (I) solution for this synthesis. The effect of several key variables that influence the shape/size of the AgNPs—concentrations of the extract relative to Ag (I), temperature, interaction time, stirring, and pH—was studied employing UV-visible spectrophotometry, scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), and x-ray diffraction (XRD). The study provides the basis for selecting processes for synthesizing AgNPs of desired shapes and sizes that can be developed using mimosa as the bioagent. All processes in this synthesis, being simple, nonpolluting, inexpensive, and nonhazardous, raise the possibility of large-scale utilization of mimosa, thereby offering a means to reduce ecological degradation that is caused by mimosa.     

Synthesis of thermoresponsive silica nanoparticle/PNIPAM hybrids by aqueous surface-initiated atom transfer radical polymerization

This paper described the synthesis of a novel kind of thermoresponsive silica nanoparticle/PNIPAM hybrids by aqueous surface-initiated atom transfer radical polymerization at room temperature. These resulting hybrid particles were characterized by FT-IR, XPS, TEM, TGA and variable temperature DLS which indicated that they owned both core/shell structures and thermoresponsiveness.     

Functional Nanoparticles Activate a Decellularized Liver Scaffold for Blood Detoxification

Extracorporeal devices have great promise for cleansing the body of virulence factors that are caused by venomous injuries, bacterial infections, and biological weaponry. The clinically used extracorporeal devices, such as artificial liver‐support systems that are mainly based on dialysis or electrostatic interaction, are limited to remove a target toxin. Here, a liver‐mimetic device is shown that consists of decellularized liver scaffold (DLS) populated with polydiacetylene (PDA) nanoparticles. DLS has the gross shape and 3D architecture of a liver, and the PDA nanoparticles selectively capture and neutralize the pore‐forming toxins (PFTs). This device can efficiently and target‐orientedly remove PFTs in human blood ex vivo without changing blood components or activating complement factors, showing potential application in antidotal therapy. This work provides a proof‐of‐principle for blood detoxification by a nanoparticle‐activated DLS, and can lead to the development of future medical devices for antidotal therapy.     

Synthesis of protein–gold nanoparticle hybrid and gold nanoplates in protein aggregates

A straightforward and economically viable approach was developed to biomimetic synthesis of gold nanocrystals by using casein micelles (CMs) without additional reductant. The UV–vis, TEM, SAED, FTIR, DLS and XRD techniques were employed to systematically characterize Au nanocrystals synthesized. Isotropic gold nanoparticle (GNP) and gold nanoplates in good yields (up to 90%) with different sizes can be obtained easily by adjusting the experimental condition. Spherical nanoparticles were obtained with tunable mean sizes at higher pH and casein concentrations. The high colloidal stability of the spherical GNP is attributed to the formation of CM/GNP hybrid under some experimental condition. At lower pH, reaction temperature and casein concentrations, single-crystalline gold nanoplates in good yields (up to 90%) are obtained. The growth of these nanostructures is attributed to an interplay between the faceting tendency of the protein molecules/micelles and the growth kinetics. More importantly, the morphological evolution of large gold nanoplates at different reaction times has been followed, and compared with some earlier protein systems, different formation mechanisms in casein micelles are obtained. The results demonstrate that both the property of individual protein molecules and protein aggregates play important roles in controlling the formation of gold nanocrystals by using amphiphilic protein.     

Determination of the size of water-soluble nanoparticles and quantum dots by field-flow fractionation

Field flow fractionation (FFF) technique is used to determine the size of water-soluble Au, ZnS, ZnS-Mn2+ nanoparticles, and CdSe, CdSe-DNA quantum dots (QDs). The results of the FFF measurements are compared with the particle size analysis using conventional techniques like scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS) studies. Water-soluble gold nanoparticles (AuNPs) stabilized by mercaptosuccinic acid (MSA) as the ligand when analyzed by the SEM and DLS showed evidence of extensive aggregation, preventing an accurate determination of the average particle size. The TEM analyses without staining offered a facile measurement of the nanoparticle core but average particle size determination required analysis of the TEM image using image analysis software. On the other hand the FFF is seemingly a convenient and easy method for the determination of the average particle size of the AuNPs. In case of the ZnS and ZnS-Mn2+ nanoparticles with mercaptopropionic acid (MPA) as the capping agent severe aggregation prevented accurate estimation of particle sizes even by the high resolution TEM (HRTEM), where as the size determination by the FFF was very facile. Analysis of the CdSe-DNA conjugate by the TEM was difficult as the sample got damaged upon exposure to the electron beam. The FFF cross-flow condition is apparently noninvasive and hence the technique was very effective in characterizing the CdSe-DNA QDs. Furthermore, using this simple technique it was possible to fractionate a sample of the AuNPs. The FFF measurement of water-soluble nanoparticles is an excellent complement to characterization of such particles by the conventional tools.     

Characterization and stability of liposome-enveloped trypsin/Fe3O4 for drug delivery and drug release behavior

Liposome encapsulating Fe3O4 (liposome complexes) has been prepared for targeting a drug to a specific organ, as well as for MRI (magnetic resonance imaging) contrast agents. The objective of the present work was to investigate the Fe3O4 properties and the effects of chitosan concentration on the characteristics of chitosan-coated liposome complexes. They were characterized by DLS, FT-IR, XRD, VSM, UV-Vis spectrometer, TEM and phase-contrast microscopy. The average liposome complex size was approximately 500 nm, with individual Fe3O4 nanoparticle sizes of 10 nm. The drug incorporation efficiency of trypsin in liposome complexes was 65-69%, the drug release was sustained and the incorporated drugs had the magnetization properties of the liposome complexes. Incorporation of chitosan into the liposome bilayer decreased trypsin release from the liposome complexes due to an increased rigidity of the liposome membrane structure. Chitosan-coated liposome complexes showed a higher stability when compared with the stability of non-coated liposome complexes.     

Determination of nanoparticle dimensions in colloidal solutions with elemental analysis in an electrothermal atomic-absorption spectrometer

A method is proposed for evaluating nanoparticle dimensions based on the difference in atomization kinetics for true and colloidal solutions in graphite furnaces of atomic-absorption spectrometers. The method makes it possible not only to analyze the elemental composition of colloidal nanoparticles, but also to determine their dimensions. It is proven for spherical colloidal gold particles.     

Dielectric investigations and theoretical calculations of size effect in lead titanate nanocrystals

The dielectric properties of nanograin ferroelectric lead titanate crystals are presented. The PbTiO3 samples were prepared by pressing nanopowders into plates and were studied experimentally by dielectric permittivity measurements in a wide frequency and temperature range. The TC dependence obtained showed a critical change of behavior with increasing mean nanoparticle size in the 9-nm region. The theoretical calculations based on Monte Carlo simulation were performed to describe the behavior of this material. It was shown that the distribution of nanoparticle sizes in the sample taken into account with the Monte Carlo method describes the dielectric properties of PbTiO3 nanocrystals quite well.     

Particle-size and velocity measurements in flowing conditions using dynamic light scattering

The noninvasive optical technique of dynamic light scattering (DLS) is routinely used to characterize dilute and transparent submicrometer particle dispersions in laboratory environments. A variety of industrial and biological applications would, however, greatly benefit from on-line monitoring of dispersions under flowing conditions. We present a model experiment to study flowing dispersions of polystyrene latex particles of varying sizes under varying flow conditions by using a newly developed fiber-optic DLS probe. A modified correlation function proposed in an earlier study is applied to the analysis of extracting the size and velocity of laminar flowing particulate dispersions. The complementary technique of laser Doppler velocimetry is also used to measure the speed of moving particles to confirm the DLS findings.     

Platinum nanoparticles on carbonaceous materials: the effect of support geometry on nanoparticle mobility, morphology, and melting

Molecular dynamics simulations have been used to investigate the morphology and mobility of platinum nanoparticles of various sizes supported by carbon materials. The embedded-atom method was used to model Pt-Pt interactions, and the Lennard-Jones potential was used to model the Pt-C interactions. The C?atoms in the supports were held fixed during the simulations. The supports considered were a single graphite sheet and three bundles of carbon nanotubes. Three sizes of Pt nanoparticles were considered: 130?atoms, 249?atoms, and 498?atoms (Pt(130), Pt(249), and Pt(498) respectively). It was found that for all three sizes, diffusion coefficients were approximately one order of magnitude higher for graphite-supported nanoparticles than for carbon nanotube-supported nanoparticles. In addition, increasing the size of the nanoparticle decreased its diffusion coefficient, with Pt(130) having the highest and Pt(498) the lowest diffusion coefficients. More interestingly, we found that for the Pt nanoparticles of all three sizes the diffusion coefficient increases as temperature increases, reaches a maximum at the melting temperature of the nanoparticle, and then decreases. The melting temperature was found to be strongly dependent on the particle size, but only slightly dependent on the features of the supports. While the size of the nanoparticle was seen to affect the particles' mobility, it did not significantly affect their structure. The nanoparticles supported by graphite have density profiles that indicate a highly ordered, fcc-like structure, while the particles supported by carbon nanotubes have a more disordered structure. An order parameter confirms that the nanoparticles' structure depends on the support morphology.     

Gold nanoparticle-based simple colorimetric and ultrasensitive dynamic light scattering assay for the selective detection of Pb(II) from paints, plastics, and water samples

Pb (II) is a common water pollutant with high toxicity. According to the CDC, about 310,000 U.S. children of ages 1-5 have high levels of lead in their blood that it is due to the exposure to lead from plastic toys and other products. As a result, the development of ultrasensitive assays for the real-time detection of Pb(II) from plastic toys and paints is very important for water controlling, clinical toxicology and industrial processes. Driven by the need to detect trace amounts of Pb(II) from water samples, we report a label-free, highly selective and ultra sensitive glutathione modified gold nanoparticle based dynamic light scattering (DLS) probe for Pb(II) recognition in 100 ppt level from aqueous solution with excellent discrimination against other heavy metals. The sensitivity of our assay to detect Pb(II) level in water is almost 2 orders of magnitude higher than the EPA standard limit. We have also demonstrated that our DLS assay is capable of measuring the amount of Pb(II) in paint, plastic toys, and water from MS river. A possible mechanism and operating principles of our DLS assay have been discussed. Ultimately, this nanotechnology driven assay could have enormous potential applications in rapid, on-site monitoring of Pb(II) from day-to-day sample.