Emerging techniques for submicrometer particle sizing applied to Stöber silica.

The accurate characterization of submicrometer and nanometer sized particles presents a major challenge in the diverse applications envisaged for them including cosmetics, biosensors, renewable energy, and electronics. Size is one of the principal parameters for classifying particles and understanding their behavior, with other particle characteristics usually only quantifiable when size is accounted for. We present a comparative study of emerging and established techniques to size submicrometer particles, evaluating their sizing precision and relative resolution, and demonstrating the variety of physical principles upon which they are based, with the aim of developing a framework in which they can be compared. We used in-house synthesized Stöber silica particles between 100 and 400 nm in diameter as reference materials for this study. The emerging techniques of scanning ion occlusion sensing (SIOS), differential centrifugal sedimentation (DCS), and nanoparticle tracking analysis (NTA) were compared to the established techniques of transmission electron microscopy (TEM), scanning mobility particle sizing (SMPS), and dynamic light scattering (DLS). The size distributions were described using the mode, arithmetic mean, and standard deviation. Uncertainties associated with the six techniques were evaluated, including the statistical uncertainties in the mean sizes measured by the single-particle counting techniques. Q-Q plots were used to analyze the shapes of the size distributions. Through the use of complementary techniques for particle sizing, a more complete characterization of the particles was achieved, with additional information on their density and porosity attained.

[1]  Jennifer D. Goss,et al.  Fractionating nanosilver: importance for determining toxicity to aquatic test organisms. , 2010, Environmental science & technology.

[2]  G. Lespes,et al.  Hyphenated analytical techniques for multidimensional characterisation of submicron particles: a review. , 2011, Analytica chimica acta.

[3]  R. Piñol,et al.  Stimuli-responsive poly(4-vinyl pyridine) hydrogel nanoparticles: synthesis by nanoprecipitation and swelling behavior. , 2010, Journal of colloid and interface science.

[4]  J. Simpson,et al.  Carbon Nanotubes: Measuring Dispersion and Length , 2011, Advanced materials.

[5]  Tianbo Liu,et al.  Characterization of Nanoparticles by Scattering Techniques , 2000 .

[6]  Martin Hassellöv,et al.  Applications of particle-tracking analysis to the determination of size distributions and concentrations of nanoparticles in environmental, biological and food samples , 2011 .

[7]  G. Cavaletti,et al.  Recent development, applications, and perspectives of mesoporous silica particles in medicine and biotechnology. , 2009, Current medicinal chemistry.

[8]  Alok Dhawan,et al.  Toxicity assessment of nanomaterials: methods and challenges , 2010, Analytical and bioanalytical chemistry.

[9]  H. Cölfen,et al.  Analytical ultracentrifugation of colloids. , 2010, Nanoscale.

[10]  Hermann Nirschl,et al.  Comparison of Nanometric Particle Size Distributions as Determined by SAXS, TEM and Analytical Ultracentrifuge , 2009 .

[11]  W. Ford,et al.  Surface modification of colloidal silica , 1990 .

[12]  G de With,et al.  Biomimetic superhydrophobic and highly oleophobic cotton textiles. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[13]  F. Galembeck,et al.  ESI-TEM imaging of surfactants and ions sorbed in Stöber silica nanoparticles. , 2006, Langmuir.

[14]  H. Coll,et al.  Determination of gelatin-layer thickness on AgBr by means of a disk centrifuge , 1985 .

[15]  James F. Ranville,et al.  Nanoparticle analysis and characterization methodologies in environmental risk assessment of engineered nanoparticles , 2008, Ecotoxicology.

[16]  François Huaux,et al.  Influence of size, surface area and microporosity on the in vitro cytotoxic activity of amorphous silica nanoparticles in different cell types , 2010, Nanotoxicology.

[17]  Charles F. Zukoski,et al.  Preparation of monodisperse silica particles: control of size and mass fraction , 1988 .

[18]  R. Crooks,et al.  Comparison of nanoparticle size and electrophoretic mobility measurements using a carbon-nanotube-based coulter counter, dynamic light scattering, transmission electron microscopy, and phase analysis light scattering. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[19]  J. W. Jansen,et al.  Preparation and characterization of spherical monodisperse silica dispersions in nonaqueous solvents , 1981 .

[20]  Stefan Tenzer,et al.  Nanoparticle size is a critical physicochemical determinant of the human blood plasma corona: a comprehensive quantitative proteomic analysis. , 2011, ACS nano.

[21]  R. W. Lines,et al.  The Electrical Sensing Zone Method (The Coulter Principle) , 1992 .

[22]  J. Vermant,et al.  Flow dichroism as a reliable method to measure the hydrodynamic aspect ratio of gold nanoparticles. , 2011, ACS nano.

[23]  S. Rigby,et al.  Engineering silica particles as oral drug delivery vehicles. , 2008, Current pharmaceutical design.

[24]  K. Ulbrich,et al.  Core-crosslinked polymeric micelles with controlled release of covalently entrapped doxorubicin. , 2010, Biomaterials.

[25]  Callaway Brown Particle-size Distributions by Centrifugal Sedimentation , 1944 .

[26]  Y. Wang,et al.  Spherical antireflection coatings by large-area convective assembly of monolayer silica microspheres , 2009 .

[27]  Werner Österle,et al.  Characterisation of silica nanoparticles prior to in vitro studies: from primary particles to agglomerates , 2011 .

[28]  D D Allen,et al.  Nanoparticle Technology for Drug Delivery Across the Blood-Brain Barrier , 2002, Drug development and industrial pharmacy.

[29]  Jin Young Kim,et al.  Determination of nanoparticle size distribution together with density or molecular weight by 2D analytical ultracentrifugation , 2011, Nature communications.

[30]  Robert D. Boyd,et al.  New approach to inter-technique comparisons for nanoparticle size measurements; using atomic force microscopy, nanoparticle tracking analysis and dynamic light scattering. , 2011 .

[31]  Nathalie Tufenkji,et al.  Characterizing manufactured nanoparticles in the environment: multimethod determination of particle sizes. , 2009, Environmental science & technology.

[32]  Vikas Mittal,et al.  Correcting for a density distribution: particle size analysis of core-shell nanocomposite particles using disk centrifuge photosedimentometry. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[33]  William D Pyrz,et al.  Particle size determination using TEM: a discussion of image acquisition and analysis for the novice microscopist. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[34]  Joseph M Slocik,et al.  Colorimetric response of peptide-functionalized gold nanoparticles to metal ions. , 2008, Small.

[35]  Montserrat Filella,et al.  Analytical applications of photon correlation spectroscopy for size distribution measurements of natural colloidal suspensions: capabilities and limitations , 1997 .

[36]  S. McDonald,et al.  Determination of the true size of poly(vinyl chloride) latices by electron microscopy using a vertical shadowing technique , 1977 .

[37]  P. Schurtenberger,et al.  Hydrodynamic properties of magnetic nanoparticles with tunable shape anisotropy: prediction and experimental verification. , 2011, The journal of physical chemistry. B.

[38]  M. Delville,et al.  Growth of monodisperse mesoscopic metal-oxide colloids under constant monomer supply. , 2005, Physical review. E, Statistical, nonlinear, and soft matter physics.

[39]  Brian G. Trewyn,et al.  Mesoporous Silica Nanoparticles for Drug Delivery and Biosensing Applications , 2007 .

[40]  H. Müller,et al.  Simultaneous determination of particle and density distributions of dispersions by analytical ultracentrifugation , 1995 .

[41]  B. R. Jennings,et al.  Particle size measurement: the equivalent spherical diameter , 1988, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[42]  Richard M Crooks,et al.  The resurgence of Coulter counting for analyzing nanoscale objects. , 2004, The Analyst.

[43]  Kevin Ke,et al.  Label-free affinity assays by rapid detection of immune complexes in submicrometer pores. , 2006, Angewandte Chemie.

[44]  M. Baalousha,et al.  Supramolecular structure of humic acids by TEM with improved sample preparation and staining , 2005, Microscopy research and technique.

[45]  Gary Bryant,et al.  Improved Particle Size Distribution Measurements Using Multiangle Dynamic Light Scattering , 1995 .

[46]  M. Brook,et al.  Colloidal Stability of Stöber Silica in Acetone , 1996 .

[47]  A. Malloy,et al.  NanoParticle Tracking Analysis; The Halo System , 2006 .

[48]  Saber M Hussain,et al.  Characterization of nanomaterial dispersion in solution prior to in vitro exposure using dynamic light scattering technique. , 2008, Toxicological sciences : an official journal of the Society of Toxicology.

[49]  Dong Liang,et al.  Influence of anchoring ligands and particle size on the colloidal stability and in vivo biodistribution of polyethylene glycol-coated gold nanoparticles in tumor-xenografted mice. , 2009, Biomaterials.

[50]  S. Bon,et al.  Unraveling mechanistic events in solids-stabilized emulsion polymerization by monitoring the concentration of nanoparticles in the water phase. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[51]  M. Trau,et al.  Tunable nano/micropores for particle detection and discrimination: scanning ion occlusion spectroscopy. , 2010, Small.

[52]  W. Stöber,et al.  Controlled growth of monodisperse silica spheres in the micron size range , 1968 .

[53]  Robert Gurny,et al.  Nanoparticles for drug delivery: the need for precision in reporting particle size parameters. , 2008, European journal of pharmaceutics and biopharmaceutics : official journal of Arbeitsgemeinschaft fur Pharmazeutische Verfahrenstechnik e.V.

[54]  Alla Zelenyuk,et al.  From Agglomerates of Spheres to Irregularly Shaped Particles: Determination of Dynamic Shape Factors from Measurements of Mobility and Vacuum Aerodynamic Diameters , 2006 .

[55]  T. Hasegawa,et al.  Three-dimensional nano-structure of in situ silica in natural rubber as revealed by 3D-TEM/electron tomography , 2005 .

[56]  Boris N. Khlebtsov,et al.  Observation of Extra-High Depolarized Light Scattering Spectra from Gold Nanorods , 2008 .

[57]  J. W. Kim,et al.  Size control of silica nanoparticles and their surface treatment for fabrication of dental nanocomposites. , 2007, Biomacromolecules.

[58]  P. Marchot,et al.  Study of the texture of monodisperse silica sphere samples in the nanometer size range , 1986 .

[59]  H. Sakurai,et al.  Metrology of airborne and liquid-borne nanoparticles: current status and future needs , 2010 .

[60]  F. Neville,et al.  Fabrication and activity of silicate nanoparticles and nanosilicate-entrapped enzymes using polyethyleneimine as a biomimetic polymer. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[61]  Hugo Jean Marie Demeyere,et al.  PARTICLE SIZING BY PHOTON-CORRELATION SPECTROSCOPY .4. RESOLUTION OF BIMODALS AND COMPARISON WITH OTHER PARTICLE SIZING METHODS. , 1993 .

[62]  Scott C. Brown,et al.  Research strategies for safety evaluation of nanomaterials. Part VI. Characterization of nanoscale particles for toxicological evaluation. , 2006, Toxicological sciences : an official journal of the Society of Toxicology.

[63]  F. Galembeck,et al.  Size Effects on the Microchemistry and Plasticity of Stöber Silica Particles: A Study Using EFTEM, FESEM, and AFM-SEPM Microscopies , 2001 .

[64]  G. Roebben,et al.  Interlaboratory comparison of size and surface charge measurements on nanoparticles prior to biological impact assessment , 2011 .

[65]  T. Narayanan,et al.  Time-resolved SAXS study of nucleation and growth of silica colloids , 2002 .

[66]  M. McGuire,et al.  ATR-FTIR observations of water structure in colloidal silica: implications for the hydration force mechanism. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[67]  Fernando Galembeck,et al.  Size Dependence of Stöber Silica Nanoparticle Microchemistry , 2003 .

[68]  T. Xia,et al.  Toxic Potential of Materials at the Nanolevel , 2006, Science.

[69]  B. De Baets,et al.  Accurate particle size distribution determination by nanoparticle tracking analysis based on 2-D Brownian dynamics simulation. , 2010, Journal of colloid and interface science.

[70]  Paul Quincey,et al.  Effect of nanoparticle concentration on zeta-potential measurement results and reproducibility , 2010 .

[71]  K. Johnston,et al.  Drug nanoparticles by antisolvent precipitation: mixing energy versus surfactant stabilization. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[72]  S. Provencher A constrained regularization method for inverting data represented by linear algebraic or integral equations , 1982 .

[73]  Paul Rees,et al.  Statistical analysis of nanoparticle dosing in a dynamic cellular system. , 2011, Nature nanotechnology.

[74]  B. van Ravenzwaay,et al.  Inhalation toxicity of multiwall carbon nanotubes in rats exposed for 3 months. , 2009, Toxicological sciences : an official journal of the Society of Toxicology.

[75]  Etienne Durand,et al.  Cytotoxicity and oxidative stress induced by different metallic nanoparticles on human kidney cells , 2011, Particle and Fibre Toxicology.

[76]  Peter Nordlander,et al.  Electron energy-loss spectroscopy (EELS) of surface plasmons in single silver nanoparticles and dimers: influence of beam damage and mapping of dark modes. , 2009, ACS nano.

[77]  D. J. Norris,et al.  Avoiding cracks in self-assembled photonic band-gap crystals , 2004 .

[78]  A. Alivisatos Semiconductor Clusters, Nanocrystals, and Quantum Dots , 1996, Science.

[79]  José Luis Alessandrini,et al.  Particle Size Distributions from Static Light Scattering with Regularized Non‐Negative Least Squares Constraints , 2006 .

[80]  Matt Trau,et al.  Advances in Resistive Pulse Sensors: Devices bridging the void between molecular and microscopic detection. , 2011, Nano today.

[81]  R. Pugh,et al.  Silica nanoparticle sols 1. Surface chemical characterization and evaluation of the foam generation (foamability). , 2007, Journal of colloid and interface science.

[82]  Gary W. Fuller,et al.  A large reduction in airborne particle number concentrations at the time of the introduction of “sulphur free” diesel and the London Low Emission Zone , 2012 .

[83]  R. Gnanadesikan,et al.  Probability plotting methods for the analysis of data. , 1968, Biometrika.