Optical manipulation and characterisation of aerosol particles using a single-beam gradient force optical trap

The application of optical tweezers (a single-beam gradient force optical trap) to the manipulation and characterisation of aerosol particles is discussed in this tutorial review. Optical tweezers allow not only the indefinite control over a single droplet, but control over arrays of particles. Typical particle sizes span the 1-10 microm diameter range. When coupled with spectroscopic techniques for probing evolving particle size (with nanometre accuracy), composition, phase and mixing state, detailed investigations of the thermodynamic properties of aerosol, the kinetics of particle transformation, and the nature of interparticle forces and coagulation can be undertaken.     

Controlling and characterizing the coagulation of liquid aerosol droplets

We demonstrate that optical tweezers can be used to control and characterize the coagulation and mixing state of aerosols. Liquid aerosol droplets of 2-14 mum in diameter are optically trapped and characterized by spontaneous and stimulated Raman scatterings, which together provide a unique signature of droplet size and composition. From the conventional bright field image, the size of the trapped droplet can be estimated and compared with that determined from stimulated Raman scattering, and the motion of the particle within the trapping plane can be recorded. A maximum of four droplets can be manipulated in tandem by forming multiple optical traps through rapid beam steering. The coagulation of two droplets can be studied directly by controlling two droplets. The limiting conditions under which optical forces and capillary forces dominate the aerosol coagulation event are explored by varying the relative optical trap strengths and characterizing the coagulation of different droplet sizes. Finally, we demonstrate that the coagulation of different aerosol components can be compared and the mixing state of the final coagulated droplet can be investigated. In particular, we compare the outcome of the coagulation of an aqueous sodium chloride aerosol droplet with a second aqueous droplet, with an ethanol droplet or with a decane droplet.     

A strategy for characterizing the mixing state of immiscible aerosol components and the formation of multiphase aerosol particles through coagulation

We demonstrate that the coagulation of two aerosol droplets of different chemical composition can be studied directly through the unique combination of optical tweezers and Raman spectroscopy. Multiple optical traps can be established, allowing the manipulation of multiple aerosol droplets. Spontaneous Raman scattering allows the characterization of droplet composition and mixing state, permitting the phase segregation of immiscible components in multiphase aerosol to be investigated with spatial resolution. Stimulated Raman scattering allows the integrity of the droplet and uniformity of refractive index to be probed. The combination of these spectroscopic probes with optical tweezers is shown to yield unprecedented detail in studies of the coagulation of decane and water droplets.     

Phase, morphology, and hygroscopicity of mixed oleic acid/sodium chloride/water aerosol particles before and after ozonolysis

Aerosol optical tweezers are used to probe the phase, morphology, and hygroscopicity of single aerosol particles consisting of an inorganic component, sodium chloride, and a water insoluble organic component, oleic acid. Coagulation of oleic acid aerosol with an optically trapped aqueous sodium chloride droplet leads to formation of a phase-separated particle with two partially engulfed liquid phases. The dependence of the phase and morphology of the trapped particle with variation in relative humidity (RH) is investigated by cavity enhanced Raman spectroscopy over the RH range <5% to >95%. The efflorescence and deliquescence behavior of the inorganic component is shown to be unaffected by the presence of the organic phase. Whereas efflorescence occurs promptly (<1 s), the deliquescence process requires both dissolution of the inorganic component and the adoption of an equilibrium morphology for the resulting two phase particle, occurring on a time-scale of <20 s. Comparative measurements of the hygroscopicity of mixed aqueous sodium chloride/oleic acid droplets with undoped aqueous sodium chloride droplets show that the oleic acid does not impact on the equilibration partitioning of water between the inorganic component and the gas phase or the time response of evaporation/condensation. The oxidative aging of the particles through reaction with ozone is shown to increase the hygroscopicity of the organic component.     

Characterizing the formation of organic layers on the surface of inorganic/aqueous aerosols by Raman spectroscopy

We demonstrate that nonlinear Raman spectroscopy coupled with aerosol optical tweezers can be used to probe the evolving phase partitioning in mixed organic/inorganic/aqueous aerosol droplets that adopt a core-shell structure in which the aqueous phase is coated in an organic layer. Specifically, we demonstrate that the characteristic fingerprint of wavelengths at which stimulated Raman scattering is observed can be used to assess the phase behavior of multiphase decane/aqueous sodium chloride droplets. Decane is observed to form a layer on the surface of the core aqueous droplet, and from the spectroscopic signature the aqueous core size can be determined with nanometer accuracy and the thickness of the decane layer with an accuracy of +/-8 nm. Further, the presence of the organic layer is observed to reduce the rate at which water evaporates from the core of the droplet with an increasing rate of evaporation observed with diminishing layer thickness.     

Ultrasensitive absorption spectroscopy of optically-trapped aerosol droplets

High-sensitivity optical absorption measurements on individual sub-picoliter aqueous droplets are reported using aerosol optical tweezers to simultaneously manipulate and characterize a sample droplet and a control droplet for comparison. It is demonstrated that the detection sensitivity to trace analytes is set by the weak absorption by the solvent, water, and that absorbances less than 5 x 10(-7) can be measured over pathlengths of less than 10 microm. The potential applications of this approach to analyze aerosol particle composition and to perform trace analysis are discussed.     

Direct comparison of the hygroscopic properties of ammonium sulfate and sodium chloride aerosol at relative humidities approaching saturation

Holographic optical tweezers are used to make comparative measurements of the hygroscopic properties of single component aqueous aerosol containing sodium chloride and ammonium sulfate over a range of relative humidity from 84% to 96%. The change in RH over the course of the experiment is monitored precisely using a sodium chloride probe droplet with accuracy better than ±0.09%. The measurements are used to assess the accuracy of thermodynamic treatments of the relationship between water activity and solute mass fraction with particular attention focused on the dilute solute limit approaching saturation vapor pressure. The consistency of the frequently used Clegg-Brimblecombe-Wexler (CBW) treatment for predicting the hygroscopic properties of sodium chloride and ammonium sulfate aerosol is confirmed. Measurements of the equilibrium size of ammonium sulfate aerosol are found to agree with predictions to within an uncertainty of ±0.2%. Given the accuracy of treating equilibrium composition, the inconsistencies highlighted in recent calibration measurements of critical supersaturations of sodium chloride and ammonium sulfate aerosol cannot be attributed to uncertainties associated with the thermodynamic predictions and must have an alternative origin. It is concluded that the CBW treatment can allow the critical supersaturation to be estimated for sodium chloride and ammonium sulfate aerosol with an accuracy of better than ±0.002% in RH. This corresponds to an uncertainty of ≤1% in the critical supersaturation for typical supersaturations of 0.2% and above. This supports the view that these systems can be used to accurately calibrate instruments that measure cloud condensation nuclei concentrations at selected supersaturations. These measurements represent the first study in which the equilibrium properties of two particles of chemically distinct composition have been compared simultaneously and directly alongside each other in the same environment.     

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.     

Comparison of the accuracy of aerosol refractive index measurements from single particle and ensemble techniques

The ability of two techniques, aerosol cavity ring down spectroscopy (A-CRDS) and optical tweezers, to retrieve the refractive index of atmospherically relevant aerosol was compared through analysis of supersaturated sodium nitrate at a range of relative humidities. Accumulation mode particles in the diameter range 300-600 nm were probed using A-CRDS, with optical tweezer measurements performed on coarse mode particles several micrometers in diameter. A correction for doubly charged particles was applied in the A-CRDS measurements. Both techniques were found to retrieve refractive indices in good agreement with previously published results from Tang and Munkelwitz, with a precision of ±0.0012 for the optical tweezers and ±0.02 for the A-CRDS technique. The coarse mode optical tweezer measurements agreed most closely with refractive index predictions made using a mass-weighted linear mixing rule. The uncertainty in the refractive index retrieved by the A-CRDS technique prevented discrimination between predictions using both mass-weighted and volume-weighted linear mixing rules. No efflorescence or kinetic limitations on water transport between the particle and the gas phase were observed at relative humidities down to 14%. The magnitude of the uncertainty in refractive index retrieved using the A-CRDS technique reflects the challenges in determining particle optical properties in the accumulation mode, where the extinction efficiency varies steeply with particle size.     

Evaporation of ethanol/water droplets: examining the temporal evolution of droplet size, composition and temperature

The evolving size, composition, and temperature of evaporating ethanol/water aerosol droplets 25-57 microm in radius are probed by cavity enhanced Raman scattering (CERS) and laser induced fluorescence. This represents the first study in which the evolving composition of volatile droplets has been probed with spatial selectivity on the millisecond time scale, providing a new strategy for exploring mass and heat transfer in aerosols. The Raman scattering intensity is shown to depend exponentially on species concentration due to the stimulated nature of the CERS technique, providing a sensitive measure of the concentration of the volatile ethanol component. The accuracy with which we can determine droplet size, composition, and temperature is discussed. We demonstrate that the CERS measurements of evolving size and composition of droplets falling in a train can be used to characterize, and thus avoid, droplet coagulation. By varying the surrounding gas pressure (7-77 kPa), we investigate the dependence of the rate of evaporation on the rate of gas diffusion, and behavior consistent with gas diffusion-limited evaporation is observed. We suggest that such measurements can allow the determination of the vapor pressures of components within the droplet and can allow the determination of activity coefficients of volatile species.     

Characterizing multiphase organic/inorganic/aqueous aerosol droplets

The partitioning of an immiscible and volatile organic component between the gas and aqueous condensed phases of an aerosol is investigated using optical tweezers. Specifically, the phase segregation of immiscible decane and aqueous components within a single liquid aerosol droplet is characterized by brightfield microscopy and by spontaneous and stimulated Raman scattering. The internally mixed phases are observed to adopt equilibrium geometries that are consistent with predictions based on surface energies and interfacial tensions and the volume fractions of the two immiscible phases. In the limit of low organic volume fraction, the stimulated Raman scattering signature is consistent with the formation of a thin film or lens of the organic component on the surface of an aqueous droplet. By comparing the nonlinear spectroscopic signature with Mie scattering predictions for a core-shell structure, the thickness of the organic layer can be estimated with nanometer accuracy. Time-dependent measurements allow the evolving partitioning of the volatile organic component between the condensed and vapor phases to be investigated.     

Digital microfluidics and delivery of molecular payloads with magnetic porous silicon chaperones

Digital microfluidics involves the manipulation of molecules and materials in discrete packages. This paper reviews our work using amphiphilic magnetic microparticles constructed from porous silicon. An individual porous particle can be used to carry a nanomole or smaller quantities of a reagent, and assemblies of the particles can encapsulate and transport microliter droplets of liquid containing inorganic, organic, or biological molecules. The tracking and identification of each particle can be accomplished with spectral labels that are encoded into the particles during their synthesis. When used to chaperone liquid droplets, the labels can identify the separate droplets prior to mixing and also the combined droplets after mixing. Magnetic iron oxide nanoparticles encapsulated in the porous matrix allow the manipulation of the particles or whole droplet assemblies with a magnetic field, and they also allow heating of the particle's payload by means of an externally applied RF field. Examples of organic, inorganic, and biomolecular addition reactions, catalytic reactions, and thermolysis reactions are described.     

A unified platform for optoelectrowetting and optoelectronic tweezers

A platform capable of seamlessly unifying both optoelectrowetting and optoelectronic tweezers is presented. This enables the user to manipulate aqueous droplets (with electrowetting) as well as individual particles within those droplets (with dielectrophoresis). The device requires no photolithography and droplet/particle manipulation can occur continuously over the entire surface of the device. Droplet and 10 μm polystyrene particle speeds of up to 8 mm s(-1) and 60 μm s(-1), respectively, are demonstrated. Particle concentration within, and subsequent splitting of, a droplet is performed resulting in average concentration efficiencies of 93%. Serial concentration is also demonstrated resulting in exponentially increasing particle concentrations and a 10× concentration increase. Finally, the platform is used to select a single cell out of a cohort and subsequently encapsulate it in its own aqueous droplet.     

Exploring the complexity of aerosol particle properties and processes using single particle techniques

The complex interplay of processes that govern the size, composition, phase and morphology of aerosol particles in the atmosphere is challenging to understand and model. Measurements on single aerosol particles (2 to 100 μm in diameter) held in electrodynamic, optical and acoustic traps or deposited on a surface can allow the individual processes to be studied in isolation under controlled laboratory conditions. In particular, measurements can now be made of particle size with unprecedented accuracy (sub-nanometre) and over a wide range of timescales (spanning from milliseconds to many days). The physical state of a particle can be unambiguously identified and its composition and phase can be resolved with a high degree of spatial resolution. In this review, we describe the advances made in our understanding of aerosol properties and processes from measurements made of phase behaviour, hygroscopic growth, morphology, vapour pressure and the kinetics of water transport for single particles. We also show that studies of the oxidative aging of single particles, although limited in number, can allow the interplay of these properties to be investigated. We conclude by considering the contributions that single particle measurements can continue to make to our understanding of the properties and processes occurring in atmospheric aerosol.     

Retrieval of the complex refractive index of aerosol droplets from optical tweezers measurements

The cavity enhanced Raman scattering spectrum recorded from an aerosol droplet provides a unique fingerprint of droplet radius and refractive index, assuming that the droplet is homogeneous in composition. Aerosol optical tweezers are used in this study to capture a single droplet and a Raman fingerprint is recorded using the trapping laser as the source for the Raman excitation. We report here the retrieval of the real part of the refractive index with an uncertainty of ± 0.0012 (better than ± 0.11%), simultaneously measuring the size of the micrometre sized liquid droplet with a precision of better than 1 nm (< ± 0.05% error). In addition, the equilibrium size of the droplet is shown to depend on the laser irradiance due to optical absorption, which elevates the droplet temperature above that of the ambient gas phase. Modulation of the illuminating laser power leads to a modulation in droplet size as the temperature elevation is altered. By measuring induced size changes of <1 nm, we show that the imaginary part of the refractive index can be retrieved even when less than 10 × 10(-9) with an accuracy of better than ± 0.5 × 10(-9). The combination of these measurements allows the complex refractive index of a droplet to be retrieved with high accuracy, with the possibility of making extremely sensitive optical absorption measurements on aerosol samples and the testing of frequently used mixing rules for treating aerosol optical properties. More generally, this method provides an extremely sensitive approach for measuring refractive indices, particularly under solute supersaturation conditions that cannot be accessed by simple bulk-phase measurements.     

Spectroscopy of growing and evaporating water droplets: exploring the variation in equilibrium droplet size with relative humidity

We demonstrate that the thermodynamic properties of a single liquid aerosol droplet can be explored through the combination of a single-beam gradient force optical trap with Raman spectroscopy. A single aqueous droplet, 2-6 microm in radius, can be trapped in air indefinitely and the response of the particle to variations in relative humidity investigated. The Raman spectrum provides a unique fingerprint of droplet composition, temperature, and size. Spontaneous Raman scattering is shown to be consistent with that from a bulk phase sample, with the shape of the OH stretching band dependent on the concentration of sodium chloride in the aqueous phase and on the polarization of the scattered light. Stimulated Raman scattering at wavelengths commensurate with whispering gallery modes is demonstrated to provide a method for determining the size of the trapped droplet with nanometer precision and with a time resolution of 1 s. The polarization dependence of the stimulated scatter is consistent with the dependence observed for the spontaneous scatter from the droplet. By characterizing the spontaneous and stimulated Raman scattering from the droplet, we demonstrate that it is possible to measure the equilibrium size and composition of an aqueous droplet with variation in relative humidity. For this benchmark study we investigate the variation in equilibrium size with relative humidity for a simple binary sodium chloride/aqueous aerosol, a typical representative inorganic/aqueous aerosol that has been studied extensively in the literature. The measured equilibrium sizes are shown to be in excellent agreement with the predictions of K?hler theory. We suggest that this approach could provide an important new strategy for characterizing the thermodynamic properties and kinetics of transformation of aerosol particles.     

Colored thin films prepared from hydrogel microspheres

Ordered 2-D structures composed of poly(N-isopropylacrylamide) (PNIPAM) microgel particles that had regularity on a sub-micrometer length scale were prepared. By using sterically stabilized PNIPAM microgel particles as components, the ordered array was formed by a self-assembly process. The particle array was prepared by depositing a droplet of the microgel dispersion on a substrate. Atomic force microscopy observation of the resulting thin films revealed that they comprised a monolayer particle array. The periodic structure of the array produced iridescent colors due to optical diffraction. Since a homogeneous particle array can be prepared simply by drying the dispersion, this particle dispersion may be considered as a new ink whose color is generated from the microstructure in the films produced.     

Nanoparticle modification by weak polyelectrolytes for pH-sensitive pickering emulsions

The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte.     

Microgel Capsules Tailored by Droplet‐Based Microfluidics

Microgel capsules are micrometer‐sized particles that consist of a cross‐linked, solvent‐swollen polymer network complexed with additives. These particles have various applications, such as drug delivery, catalysis, and analytics. To optimize the performance of microgel capsules, it is crucial to control their size, shape, and content of encapsulated additives with high precision. There are two classes of microgel‐capsule structures. One class comprises bulk microcapsules that consist of a polymer network spanning the entire particle and entrapping the additive within its meshes. The other class comprises core–shell structures; in this case, the microgel polymer network just forms the shell of the particles, whereas their interior is hollow and hosts the encapsulated payload. Both types of structures can be produced with exquisite control by droplet‐based microfluidic templating followed by subsequent droplet gelation. This article highlights some early and recent achievements in the use of this technique to tailor soft microgel capsules; it also discusses applications of these particles. A special focus is on the encapsulation of living cells, which are very sensitive and complex but also very useful additives for immobilization within microgel particles.     

Poly(N-vinylcaprolactam-co-glycidyl methacrylate) aqueous microgels labeled with fluorescent LaF3:Eu nanoparticles

We describe the synthesis and properties of functional microgel particles based on poly(N-vinylcaprolactam-co-glycidyl methacrylate) (PVCL/PGMA) copolymer. A series of colloidally stable microgel particles with a range of glycidyl methacrylate content were prepared by surfactant-free heterophase polymerization in water. The microgel particles obtained had hydrodynamic radii between 250 and 350 nm and were fairly monodisperse in size; however, a broadening of the particle size distribution was observed for samples with a low GMA content. The PVCL/PGMA microgel particles exhibit thermally responsive reversible changes in diameter in water, and the swelling degree increased with the PVCL fraction in the copolymer structure. These microgels were then modified with photoluminescent europium-doped lanthanum fluoride nanoparticles (LaF3:Eu-AEP) through reaction of the 2-aminoethyl phosphate surface ligands with epoxy groups present in the microgel. These hybrid microgels were colloidally stable and thermally responsive in aqueous solution.