Can the light scattering depolarization ratio of small particles be greater than 1/3?

According to the theory of light scattering by small randomly oriented particles, the depolarized ratio of the scattered intensities, I(vh)/I(vv), cannot exceed 1/3. Here we show that this conclusion does not hold for nonspherical plasmon resonant metal particles. Our analysis is based on the Rayleigh approximation and the exact T-matrix method as applied to spheroids and circular cylinders with semispherical ends. For small particles, the condition I(vh)/I(vv) >1/3 can be satisfied within the upper left quadrant of the complex relative dielectric permeability Real(eps) < -2 (rods) and within the upper unit semicircle centered at Real(eps) = -1 (disks). For gold nanorods with the axis ratio exceeding 2, the maximal theoretical values I(vh)/I(vv) lie between 1/3 and 3/4 at wavelengths of 550-650 nm. The extinction and static light scattering spectra (450-850 nm, at 90 degrees degrees) as well as the depolarized ratio of He-Ne laser light scattering were measured with gold nanospheres (the average diameters of 21, 29, and 46 nm) and nanorods (the longitudinal plasmon resonance peak positions at 655, 692, and 900 nm). The measured depolarization ratios of nanospheres (0.07-0.16) and nanorods (0.3-0.48) are in good agreement with theoretical calculations based on estimations of the average particle size and shape.     

Cavity ring-down spectroscopy measurements of single aerosol particle extinction. I. The effect of position of a particle within the laser beam on extinction

A continuous wave distributed feedback diode laser operating in the near infrared at wavelengths close to 1650 nm has been used to measure the extinction of light by single aerosol particles. The technique of optical feedback cavity ring-down spectroscopy (CRDS) was used for measurement of CRDS events at a repetition rate of 1.25 kHz. This very high repetition rate enabled multiple measurements of the extinction of light by single aerosol particles for the first time and demonstrated the dependence of light scattering on the position of a particle within the laser beam. A model is proposed to explain quantitatively this phenomenon. The minimum detectable dimensionless extinction coefficient epsilonmin was determined to be 3x10(-6). Extinction values obtained for single spherical polymer beads from a monodisperse sample of particles of diameter of 4 microm are in near-quantitative agreement with the values calculated by the Mie scattering theory. The deviations from the Mie theory expected for measurement of extinction by CRDS using a continuous wave laser are discussed in the companion paper.     

Separation and detection of individual submicron particles by capillary electrophoresis with laser-light-scattering detection

Separation and detection of individual submicron polystyrene spheres using capillary electrophoresis with laser-light-scattering detection has been demonstrated. Electrophoretically separated particles were passed through a focused laser beam and light scattered from individual particles was collected at 90 degrees. Each diameter of polystyrene spheres injected (from 110 to 992 nm) resulted in the observation of a well-defined migration window containing multiple peaks, each arising from the light scattered by an individual particle. The migration time window for individual particles of a particular size corresponded well to the migration time of a peak from a population of particles of the same size detected using a UV absorbance detector. The electrophoretic mobility and scattered light intensity were determined for each particle detected. The average scattered light intensity for each particle size was consistent with Mie scattering theory. Particles as small as 110 nm in diameter were detected individually using this method, but particles with a diameter of 57 nm could not be individually detected. The number of single particle scattering events was counted and compared to the theoretical number of particles injected electrokinetically, and the detection efficiency determined ranged from 38 to 57% for polystyrene spheres of different sizes. The laser-light-scattering detection method was directly compared to laser-induced fluorescence detection using fluorescent polystyrene microspheres. The number of particles detected individually by each method was in agreement.     

基质与分析物的摩尔比和激光能量对分析物离子信号的影响

A method of aerosol introduction for matrix-assisted laser desorption/ionization (MALDI) is described. The aerosol particles containing matrix and analyte enter directly into the aerosol time-of-flight mass spectrometer (ATOFMS) at atmospheric pressure. The scattered light signals from the aerosol particles are collected by a photomultiplier tube (PMT) and are passed on to an external electronic timing circuit, which determines particle size and is used to trigger a 266 nm pulsed Nd:YAG laser. The aerosol MALDI mass spectra and aerodynamic diameter of single particles can be obtained in real-time. Compared with other methods of liquid sample introduction, this method realizes detection of single particles and, more importantly, the sample consumption is lower. The effects of matrix-to-analyte ratio and laser pulse energy on analyte ion yield are examined. The optimal matrix-to-analyte ratio and laser energy are 50-110:1 and 200-400 μJ respectively.     

Measurements of extinction by aerosol particles in the near-infrared using continuous wave cavity ring-down spectroscopy

Cavity ring-down spectroscopy using a fiber-coupled continuous wave distributed feedback laser at a wavelength of 1520 nm has been used to measure extinction of light by samples of nearly monodisperse aerosol particles <1 μm in diameter. A model is tested for the analysis of the sample extinction that is based on the Poisson statistics of the number of particles within the intracavity laser beam: variances of measured extinction are used to derive values of the scattering cross section for size-selected aerosol particles, without need for knowledge of the particle number density or sample length. Experimental parameters that influence the performance of the CRD system and the application and limitations of the statistical model are examined in detail. Determinations are reported of the scattering cross sections for polystyrene spheres (PSSs), sodium chloride, and ammonium sulfate, and, for particles greater than 500 nm in diameter, are shown to be in agreement with the corresponding values calculated using Mie theory or Discrete Dipole Approximation methods. For smaller particles, the experimentally derived values of the scattering cross section are larger than the theoretical predictions, and transmission of a small fraction of larger particles into the cavity is argued to be responsible for this discrepancy. The effects of cubic structure on the determination of optical extinction efficiencies of sodium chloride aerosol particles are examined. Values are reported for the real components of the refractive indices at 1520 nm of PSS, sodium chloride, and ammonium sulfate aerosol particles.     

Cavity ring-down spectroscopy measurement of single aerosol particle extinction. II. Extinction of light by an aerosol particle in an optical cavity excited by a cw laser

The authors present an analytical derivation of the scattered power from a spherical, homogeneous, nonabsorbing particle in a plane standing wave. The scattered power changes significantly with the position of the particle with respect to the peaks and nodes of the standing wave, even for particles whose diameters are many times the wavelength of the light. The analysis is applicable to continuous-wave cavity ring-down spectroscopy on aerosol particles, and the structure of the standing wave is expected to affect both the measured ring-down time and the shape of the ring-down trace. The dependence of the extinction on the phase of the standing wave at the location of the particle is captured in a parameter zeta which connects the current treatment to standard Mie scattering theory. Methods for calculating zeta are presented.     

Force measurements between sub-100 nm colloidal particles

Interparticle forces have been measured between polystyrene latex particles as small as 85 nm in diameter in KCl solutions. A variant of the differential electrophoresis technique, called particle force light scattering (PFLS), was used to measure forces between Brownian, nearly touching particles for diameters from 4500 nm down to 85 nm. The forces, some less than 0.1 pN, matched to within a factor of 2 with predictions from depletion and DLVO theory.     

Elastic light scattering from nanoparticles by monochromatic vacuum-ultraviolet radiation

Elastic light scattering is reported using monochromatic vacuum-ultraviolet radiation to study free, spherical silica nanoparticles prepared by approaches from colloidal chemistry, with diameters between 100 and 240 nm. The colloidal nanoparticles of defined size are transferred from an aqueous solution into the gas phase using a particle beam experiment. After focusing of the particle beam by an aerodynamic lens, the scattered light from monochromatic synchrotron radiation is measured. Angle-resolved elastically scattered light is detected, showing a strong forward-scattering component. Additional evidence for the detection of elastically scattered light comes from plotting the scattered light intensity as a function of the dimensionless parameter qR, where q is the magnitude of the scattering wave vector and R is the particle radius. This yields different power-law regimes that are assigned to scattering from the surface and the bulk of the nanoparticles. Furthermore, there is evidence for modulations in the scattered light intensity as a function of scattering angle, which is clearly distinguished from the forward-scattering component. The experimental results are compared to Mie scattering simulations for isolated particles, yielding general agreement with the experimental results. Deviations from Mie simulations are observed for samples consisting of significant amounts of aggregates. The present results indicate that the optical properties of free nanoparticles are sensitively probed by vacuum-ultraviolet radiation.     

High-pressure liquid dispersion and fragmentation of flame-made silica agglomerates

The influence of primary particle diameter and the degree of agglomeration of flame-made silica agglomerate suspensions in aqueous solutions is studied by high-pressure dispersion (up to 1500 bar) through a nozzle with a 125 microm inner diameter. These particles were produced (4-15 g/h) by oxidation of hexamethyldisiloxane (HMDSO) in a coflow diffusion flame reactor. Their average primary particle size (10-50 nm) and degree of agglomeration were controlled by varying the oxygen and precursor flow rates. The particles were characterized by nitrogen adsorption, electron microscopy, and small-angle X-ray scattering. Hydrodynamic stresses break up soft agglomerates and yield hard agglomerate sizes in the range of 100-180 nm, as characterized by dynamic light scattering. Soft agglomerates exhibited decreasing light scattering diameters with increasing dispersion pressure, while hard agglomerates were insensitive.     

Particle formation by infrared laser ablation of glycerol: implications for ion formation

The quantity and size distribution of micrometer-sized particles ejected from thin films of glycerol were measured using light scattering particle sizing. Thin glycerol films were irradiated at atmospheric pressure with an infrared optical parametric oscillator at wavelengths between 2.95 and 3.1 microm. Particulate material resulting from the ablation was sampled directly into a particle-sizing instrument and particles with diameters greater than 500 nm were detected and sized by light scattering. The fluence threshold for particle formation was between 2000 and 3000 J/m2 for all laser wavelengths. At threshold, fewer than 100 particles/cm3 were detected and this value increased to several thousand particles/cm3 at twice the threshold fluence. The average size of the coarse particles ranged from 900 nm to 1.6 microm at threshold and decreased by 10-20% at twice the threshold fluence. The coarse particle formation observations were compared with ion formation behavior in matrix-assisted laser desorption ionization and interpreted in terms of a photomechanical mechanism for material ablation and ion formation.     

Laser-induced incandescence study on the metal aerosol particles as the effect of the surrounding gas medium

The fundamental heat transfer phenomena caused by the 1064 nm pulsed laser irradiations on the molybdenum aerosol particles were investigated by monitoring the time evolutions of the incandescence spectra using an ICCD detector with a multichannel spectrograph. The particle temperatures were evaluated from the incandescence spectra with the Planck function, and the cooling processes of the laser-heated particles were investigated. By measuring the decrease in the laser-heated particle temperatures with different surrounding media, the roles of the heat transfer processes such as vaporization, thermal radiation, and heat conduction to the surrounding media were discussed. The influences of the vaporization processes on the total heat transfer phenomena were investigated by monitoring the emissions of the constituent molybdenum atoms in the laser-induced incandescence spectra of the aerosol particles and also by investigating the relationships between the intensity of the incandescence and the fluence of the 1064 nm pulsed laser. The calculations using the theory of heat conduction suggested that the diameters of the particles produced by the photolysis of Mo(CO)6 depended on the nature of the surrounding gases.     

Chemical reactivity of two-photon excited trimethylsilylacetylene in aerosol particle formation with acrolein

Under irradiation with N₂ laser light, a gaseous mixture of trimethylsilylacetylene (ethynyltrimethylsilane) (TMeSiA) and acrolein (AC) produced sedimentary aerosol particles with a mean diameter of 1.0 μm. Nucleation process of the aerosol particles was studied by measuring monitor (He–Ne laser) light intensity scattered by the aerosol particles as formed under N₂ laser light irradiation. With increasing partial pressure of TMeSiA, the nucleation reaction of aerosol particles was accelerated due to additional generation of reactive species from TMeSiA molecules by a two-photon process. FT-IR spectra of the sedimentary particles showed that TMeSiA molecules were incorporated into polymerization reaction of AC by forming –Si–O–C– bond from R(CH₃)₂Si radicals. Two-photon processes of both AC and TMeSiA molecules under N₂ laser light irradiation were briefly discussed.     

Light-scattering form factors of asymmetric particle dimers from heteroaggregation experiments

Measurements of form factors of asymmetric particle dimers composed of oppositely charged polystyrene latex particles are presented. These measurements are based on time-resolved static and dynamic light scattering on dilute aggregating aqueous suspensions. The experimental form factors are compared with independent calculations based on the superposition T-matrix method and Rayleigh-Debye-Gans (RDG) approximation. While the RDG approximation is found to be reliable only up to particle diameters of about 250 nm, the superposition T-matrix method is very accurate for all types of dimers investigated. The present results show clearly the appropriateness of the superposition T-matrix method to estimate the optical properties of colloidal particles in the micrometer range reliably.     

Amplified light scattering and emission of silver and silver core-silica shell particles

Side versus forward light scattergrams, and fluorescence (488 nm excitation) intensity versus particle count histograms were gathered for bare, R6G-coated, and silica-R6G-coated silver particles of 150-200 nm diameter, one-by-one by flow cytometry. Fluorescence emission intensity of the composite particles monotonically increased and then reached a plateau with greater R6G concentrations, as measured by flow cytometry. Fluorescence amplification factors of up to 3.5x10(3) were estimated by reference to measurements on core-shell particles with silica instead of silver cores. Huge surface enhanced Raman scattering (SERS) intensities, at least 10(14)-fold greater than normal Raman scattering intensities, were observed with 633 nm excitation for molecules such as rhodamine 6G (R6G) on the same single particles of silver. Although routine transmission (TEM) and scanning (SEM) electron microscopies showed gross structures of the bare and coated particles, high-resolution field emission scanning electron microscopy (FE-SEM), revealed Brownian roughness describing quantum size and larger structures on the surface of primary colloidal silver particles. These silver particles were further characterized by extinction spectra and zeta potentials. Structural and light scattering observations that are reported herein were used to tentatively propose a new hierarchical model for the mechanism of SERS.     

Colloidal dynamics near a wall studied by evanescent wave light scattering: experimental and theoretical improvements and methodological limitations

The dynamics of colloidal spheres near to a wall is studied with an evanescent wave scattering setup that allows for an independent variation of the components of the scattering wave vector normal and parallel to the wall. The correlation functions obtained with this novel instrumentation are interpreted on the basis of an expression for their short time behavior that includes hydrodynamic interactions between the colloidal spheres and the wall. The combination of the evanescent wave scattering setup and the exact expression for the short time behavior of correlation functions allows for an unambiguous measurement of the particle mobility parallel and normal to the wall by means of light scattering. It is possible to measure the viscous wall drag effect on the dynamics of particles with radii as small as 27 nm, where, however, the method reaches its limits due to the low scattering intensities of such small particles.     

Particle Production in Reflection and Transmission Mode Laser Ablation: Implications for Laserspray Ionization

Particles were ablated from laser desorption and inlet ionization matrix thin films with a UV laser in reflection and transmission geometries. Particle size distributions were measured with a combined scanning mobility particle sizer (SMPS) and aerodynamic particle sizer (APS) system that measured particles in the size range from 10 nm to 20 μm. The matrixes investigated were 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), sinapic acid (SA), 2,5-dihydroxy-acetophenone (DHAP), and 2-nitrophloroglucinol (NPG). Nanoparticles with average diameters between 20 and 120 nm were observed in both transmission and reflection geometry. The particle mass distribution was significantly different in reflection and transmission geometry. In reflection geometry, approximately equal mass was distributed between particles in the 20 to 450 nm range of diameters and particles in the 450 nm to 1.5 μm diameter range. In transmission mode, the particle mass distribution was dominated by large particles in the 2 to 20 μm diameter range. Ablation of inlet ionization matrices DHAP and NPG produced particles that were 3 to 4 times smaller compared with the other matrices. The results are consistent with ion formation by nanoparticle melting and breakup or melting and breakup of the large particles through contact with heated inlet surfaces.

Relationship between scattered intensity and separation for particles in an evanescent field

We describe measurements of the scattering of visible light from an evanescent field by both spherical particles (R = 1-10 mum) that are glued to atomic force microscopy (AFM) cantilevers, and by sharp tips (R < 60 nm) that were incorporated onto the cantilevers during manufacture. The evanescent wave was generated at the interface between a flat plate and an aqueous solution, and an atomic force microscope was used to accurately control the separation, h, between the particle and the flat plate. We find that, for sharp tips, the intensity of scattered light decays exponentially with separation between the tip and the plate all the way down to h approximately 0. The measured decay length of scattered intensity, delta, is the same as the theoretical decay length of the evanescent intensity in the absence of the sharp tip. For borosilicate particles, (R = 1-10 mum), the scattering also decays exponentially with separation at large separations. However, when the separation is less than roughly 3delta, the measured scattering intensity is smaller in magnitude than that which would be predicted by extrapolating the exponential decay observed at large separations. For these particles, the scattering approximately fits the sum of two exponentials. The magnitude of the deviation from exponential at contact was roughly 10-15% for R = 1 mum particles and about 30% for larger particles and is larger for s-polarized light. Preliminary experiments on polystyrene particles shows that the scattering is also smaller than exponential at small separations but that the deviation from exponential is larger for p-polarized light. In evanescent wave AFM (EW-AFM) the scattering-separation can be calibrated for situations where the scattering is not exponential. We discuss possible errors that could be introduced by assuming that exponential decay of scattering continues down to h = 0.     

Structural Study of the Photo-Mediated Growth of Silver Nanoprisms

We present a small-angle X-ray scattering (SAXS) study of the anisotropic photoinduced growth of silver (Ag) nanoprisms in aqueous dispersions. The growth of nearly spherical (<10 nm) Ag particles into large (>40 nm) and thin (<10 nm) triangular nanoprisms induced by 550 nm laser is followed in terms of particle size using indirect and direct methods for irradiation times up to 150 min. During the process, the surface-to-volume ratio of the particles decreased. The SAXS data of the initial solution fit well to the model of polydisperse spheres with pronounced average diameters around 7.4 nm and 10 nm. The data after 45 min irradiation fit well to the model containing approximately the same amount of the initial particles and the end product, the nanoprisms.     

Counting and sizing of particles and particle agglomerates in a microfluidic device using laser light scattering: application to a particle-enhanced immunoassay

A microfluidic device for counting and sizing particles and particle agglomerates based on laser light scattering is demonstrated. The particles were confined hydrodynamically and passed through a focused laser beam. Scattering at two different angles, 15 degree and 45 degree, was detected. At an acquisition rate of 10 kHz, a throughput of 150 particles s(-1) was achieved. Scattering intensity was found to depend on particle volume for 2 to 9 microm diameter particles. Size discrimination of particles with a diameter ratio of 1: 2 was accomplished. In addition, the scattering signals of particle agglomerates formed in a particle-enhanced immunoassay for C-reactive protein (CRP) were measured. Scattering intensity was found to be dependent on the CRP concentration, 100 ng CRP per mL could be detected. The particle counting method presented is generic and can be employed in a wide variety of assays as well as for cell counting and particle counting.