Photovoltaic amorphous feroxyhyte nanostructures synthesized by atmospheric AC microplasma.

Feroxyhite (δ-FeOOH) nanomaterials were successfully synthesized through the atmospheric AC microplasma method at room temperature from ferrous sulfate aqueous solutions. Various syntheses conditions, including electric voltage, electric field strength, ferrous concentration, hydrogen peroxide concentration, and reaction duration, were systematically investigated. The synthesized products were characterized through x-ray diffraction, UV-vis absorption spectroscopy, photoluminescence spectroscopy, infra-red spectroscopy, and electron microscopy. The bandgap of the produced materials were strongly dependent of the ferrous concentration while the product ratio was dependent on all experimental conditions. The synthesis mechanism was thoroughly discussed. The synthesized nanomaterials were amorphous nanospheres, showing superparamagnetic properties at room temperature. The synthesized oxyhydroxide is a potential photovoltaic material besides its reported applications in photocatalysts and supercapacitors. The application of this synthesis technique could be extended to synthesize other oxy-hydroxide nanomaterials for renewable energy applications facilely, scalablely, cost-effectively, and environmentally.

Temperature Measurement of Trapped, Thermally Sensitive Single Particles in an Optical Trap Using Raman Spectroscopy.

Single particles trapped in an optical trap may experience temperature elevation, yet direct measurement of temperature and its distribution inside the optical trap of several to hundreds of microns in size remains a big challenge. We introduce a method that can measure the temperature inside a universal optical trap (UOT) using Raman spectroscopy of single trapped particles of high thermal conductivity. We measured temperature and temperature distributions inside the UOT using Raman shifts of single-walled carbon nanotubes (SWCNTs) and micron-sized diamonds (MSDs), which are heated by trapping laser beams directly or indirectly, depending on the location of the particle in the trap. We show that the temperature at the center of the UOT is much lower than the temperature along the hollow beams that form a hollow, cage-shaped UOT. In the range of the trapping laser power of 200-2950 mW, the surface temperature of particles trapped at the center of a UOT changes from 322 K to 830 K, correspondingly. This result gives a heating rate as a high thermal-absorbing particle trapped in the center of the UOT with 18.3 ± 0.4 °C/100 mW. In addition, the temperature gradient outside the UOT was also characterized by trapping SWCNT particles outside the UOT. Results show that when a light-absorbing particle is trapped for the study of material property, phase transitions, surface equilibrium process, chemical reactions, etc., this method can be used to measure temperature distribution and its variations in the trap and its surroundings.

A Collection of Molecular Fingerprints of Single Aerosol Particles in Air for Potential Identification and Detection Using Optical Trapping-Raman Spectroscopy.

Characterization, identification, and detection of aerosol particles in their native atmospheric states remain a challenge. Recently, optical trapping-Raman spectroscopy (OT-RS) has been developed and demonstrated for characterization of single, airborne particles. Such particles in different chemical groups have been characterized by OT-RS in recent years and many more are being studied. In this work, we collected single-particle Raman spectra measured using the OT-RS technique and began construction of a library of OT-RS fingerprints that may be used as a reference for potential detection and identification of aerosol particles in the atmosphere. We collected OT-RS fingerprints of aerosol particles from eight different categories including carbons, bioaerosols (pollens, fungi, vitamins, spores), dusts, biological warfare agent surrogates, etc. Among the eight categories, spectral fingerprints of six groups of aerosol particles have been published previously and two other groups are new. We also discussed challenges, limitations, and advantages of using single-particle optical trapping-Raman spectroscopy for aerosol-particle characterization, identification, and detection.

Measurement of circular intensity differential scattering (CIDS) from single airborne aerosol particles for bioaerosol detection and identification.

The circular intensity differential scattering (CIDS), i.e. the normalized Mueller matrix element -S14/S11, can be used to detect the helical structures of DNA molecules in biological systems, however, no CIDS measurement from single particles has been reported to date. We report an innovative method for measuring CIDS phase functions from single particles individually flowing through a scattering laser beam. CIDS signals were obtained from polystyrene latex (PSL) microspheres with or without coating of DNA molecules, tryptophan particles, and aggregates of B. subtilis spores, at the size of 3 µm in diameter. Preliminary results show that this method is able to measure CIDS phase function in tens of microseconds from single particles, and has the ability to identify particles containing biological molecules.

Active, controlled circular, and spin-rotational movement of optically trapped airborne micro-particles.

We present a novel method for actively controlling circular and/or spin-rotational motion of an optically trapped airborne micro-particle. A 532-nm Gaussian laser beam is shaped into an elliptical ring by a pair of axicons and a cylindrical lens. The shaped beam is then focused into an elliptic cone that produces an optical trap. As the cylindrical lens is rotated, a torque is exerted on the trapped particle, resulting in circular or spin-rotational motion. We show examples of the circular-rotational movement as a function of laser power and the rotation rate of the cylindrical lens.

Optical-Trapping Laser Techniques for Characterizing Airborne Aerosol Particles and Its Application in Chemical Aerosol Study.

We present a broad assessment on the studies of optically-trapped single airborne aerosol particles, particularly chemical aerosol particles, using laser technologies. To date, extensive works have been conducted on ensembles of aerosols as well as on their analogous bulk samples, and a decent general description of airborne particles has been drawn and accepted. However, substantial discrepancies between observed and expected aerosols behavior have been reported. To fill this gap, single-particle investigation has proved to be a unique intersection leading to a clear representation of microproperties and size-dependent comportment affecting the overall aerosol behavior, under various environmental conditions. In order to achieve this objective, optical-trapping technologies allow holding and manipulating a single aerosol particle, while offering significant advantages such as contactless handling, free from sample collection and preparation, prevention of contamination, versatility to any type of aerosol, and flexibility to accommodation of various analytical systems. We review spectroscopic methods that are based on the light-particle interaction, including elastic light scattering, light absorption (cavity ring-down and photoacoustic spectroscopies), inelastic light scattering and emission (Raman, laser-induced breakdown, and laser-induced fluorescence spectroscopies), and digital holography. Laser technologies offer several benefits such as high speed, high selectivity, high accuracy, and the ability to perform in real-time, in situ. This review, in particular, discusses each method, highlights the advantages and limitations, early breakthroughs, and recent progresses that have contributed to a better understanding of single particles and particle ensembles in general.

Optical-trapping of particles in air using parabolic reflectors and a hollow laser beam.

We present an advanced optical-trapping method that is capable of trapping arbitrary shapes of transparent and absorbing particles in air. Two parabolic reflectors were used to reflect the inner and outer parts of a single hollow laser beam, respectively, to form two counter-propagating conical beams and bring them into a focal point for trapping. This novel design demonstrated high trapping efficiency and strong trapping robustness with a simple optical configuration. Instead of using expensive microscope objectives, the parabolic reflectors can not only achieved large numerical aperture (N.A.) focusing, but were also able to focus the beam far away from optical surfaces to minimize optics contamination. This design also offered a large free space for flexible integration with other measuring techniques, such as optical-trapping Raman spectroscopy, for on-line single particle characterization.

Online Characterization of Single Airborne Carbon Nanotube Particles Using Optical Trapping Raman Spectroscopy.

Carbon nanotubes (CNTs) have become recognized as a potential environmental and health hazard as their applications are broadening and manufacturing costs are reducing. Fundamental information of CNTs in air is of significant importance to our understanding of their environmental fate as well as to further applications. Extensive efforts have been made over decades on characterizing CNTs; however, a majority of the studies are of bulk or CNTs dispersed on substrates. In the present study, we characterize single CNT particles in air using optical trapping Raman spectroscopy (OT-RS). Different types of CNT particles, as well as glassy carbon spheres, were optically trapped in air. Their physical properties were viewed by microscopic bright field images and scattering images; their chemical properties and structural information can be inferred from characteristic Raman bands. The system can also spatially resolve the morphology and chemical distribution of optically trapped CNT particles in air. The OT-RS technique combines single-particle morphological and chemical information and offers an online method to characterize the physicochemical properties of single CNT particles at their native states in air.

Liquid-liquid phase separation and evaporation of a laser-trapped organic-organic airborne droplet using temporal spatial-resolved Raman spectroscopy.

Chemical reactions in aerosol particles can occur between the reactive components of the particle or between the particle and its surrounding media. The fate of atmospheric aerosols depends on the environment, the composition and the distribution of components within a particle. It could be very interesting to see how a liquid aerosol particle behaves in ambient air if the particle is composed of mixed chemicals. Do the chemical components remain homogeneously mixed within a particle or separate as the mixed liquid is aerosolized? How do the chemicals within a droplet separate and interact with the air? In this paper, a single microdroplet formed from an organic-organic mixture of diethyl phthalate (DEPh) and glycerol was investigated using laser-trapped position-resolved temporal Raman spectroscopy. For the first time, we were able to directly observe the gradient distributions of the two chemicals at different positions within such an airborne droplet, their time-resolved processes of liquid-liquid phase-separation, and changes of the physical microstructure and chemical micro-composition in the droplet. The results revealed that DEPh migrated to the surface and formed an outer layer and glycerol was more concentrated in the interior of the droplet, DEPh evaporated faster than glycerol, and both organic chemicals within the mixed droplet evaporated faster than either of them within their pure droplets. This technique also provides a new method for studying the fine structure and chemical reactions of different molecules taking place inside a particle and at the interface of a particle with the surrounding microenvironment.

Optical trapping-Raman spectroscopy (OT-RS) with embedded microscopy imaging for concurrent characterization and monitoring of physical and chemical properties of single particles.

The study of physical and chemical properties of a microscopic object, such as a single particle, is made possible using optical trapping (OT) technology combined with other measuring techniques. Here we show a universal optical trap combined with Raman spectroscopy (RS) and microscopy imaging for single-particle studies. The universal optical trap is constructed using two counter-propagating hollow beams and is able to stably levitate single particles of a wide range of properties, such as transparent or absorbing materials, organic (polymers, bioaerosols, etc.) or inorganic constituents (carbon, silica, glass, etc.), and spherical or irregularly shaped morphologies. Both physical and chemical properties and their temporal evolution of the trapped particle can be characterized simultaneously using the integrated OT-RS and imaging system. We created three sample cases to demonstrate the analytical merits of the system: (I) a single particle with no change, (II) partially degraded over the measuring period, and (III) one part from the fragmentized single particle. The particles' chemical compositions, crystalline states, etc. are inferred from their Raman spectra, while their physical properties (sizes, shapes, morphologies, etc.) are revealed by images. This integrated OT-RS system provides a new approach to concurrently characterize and monitor physical and chemical properties of single micrometer-sized objects optically trapped in air.

Position-resolved Raman spectra from a laser-trapped single airborne chemical droplet.

It could be very useful to detect and monitor the molecules and molecular reactions located at different positions within a microsized particle as they respond to various micro-local environments. In this Letter, a particular optical trap using two focusing counterpropagating hollow beams was able to stably trap both absorbing and nonabsorbing particles in air for lengthy observation. A technique that can measure the Raman spectra from different submicrometer positions of a laser-trapped single airborne particle was developed. Spontaneous and stimulated Raman scattering spectra originating from different positions of a diethyl phthalate droplet were recorded, and the strong Raman scattering signals are the result of cavity-enhanced effects and the localized strong light illumination.

Detection and characterization of chemical aerosol using laser-trapping single-particle Raman spectroscopy.

Detection and characterization of the presence of chemical agent aerosols in various complex atmospheric environments is an essential defense mission. Raman spectroscopy has the ability to identify chemical molecules, but there are limited numbers of photons detectable from single airborne aerosol particles as they are flowing through a detection system. In this paper, we report on a single-particle Raman spectrometer system that can measure strong spontaneous, stimulated, and resonance Raman spectral peaks from a single laser-trapped chemical aerosol particle, such as a droplet of the VX nerve agent chemical simulant diethyl phthalate. Using this system, time-resolved Raman spectra and elastic scattered intensities were recorded to monitor the chemical properties and size variation of the trapped particle. Such a system supplies a new approach for the detection and characterization of single airborne chemical aerosol particles.

Characterization of single airborne particle extinction using the tunable optical trap-cavity ringdown spectroscopy (OT-CRDS) in the UV.

We integrated a rigid optical trap into a tunable pulsed cavity ringdown spectroscopy (OT-CRDS) system to characterize the extinction of single airborne particles in the UV spectral region (306-315 nm). Single solid particles from a multi-walled carbon nanotube (MWCNT), Bermuda grass smut spore, carbon microsphere, and blackened polyethylene microsphere were trapped in air based on the photophoretic force. The improved OT-CRDS system was highly sensitive and able to resolve extinctions of single particles from different materials and sizes at a given wavelength. Further, we successfully manipulated the number of particles, e.g., 1, 2 or more particles, in the trap and measured their distinguishable extinctions using the OT-CRDS. We also show that the particle size and extinction have a good linear correlation from the measurements of 24 single MWCNT particles. Material- and wavelength-dependent extinctions of the four types of airborne particles were also characterized. Results reveal that single airborne particles regardless of their differences in material and size, due to their heterogeneous morphology, have individual-particle dependent extinctions and that dependence can be resolved and characterized using the OT-CRDS technique.

Measurement of back-scattering patterns from single laser trapped aerosol particles in air.

We demonstrate a method for measuring elastic back-scattering patterns from single laser trapped micron-sized particles, spanning the scattering angle range of θ=167.7°-180° and φ=0°-360° in spherical coordinates. We calibrated the apparatus by capturing light-scattering patterns of 10 µm diameter borosilicate glass microspheres and comparing their scattered intensities with Lorenz-Mie theory. Back-scattering patterns are also presented from a single trapped Johnson grass spore, two attached Johnson grass spores, and a cluster of Johnson grass spores. The method has potential use in characterizing airborne aerosol particles, and may be used to provide back-scattering data for lidar applications.

Optical configurations for photophoretic trap of single particles in air.

Since Ashkin's pioneering work in the 1970's, optical trapping (OT) and manipulation have become an indispensable tool in diverse research fields. Today, there are multiple optical trapping schemes in use. In this article, we explore six different optical trapping schemes based on the photophoretic force (PPF). Within these schemes we explore 21 variants differing in such details as laser source, power, beam shape, and focusing optics. We evaluate and rate the trapping quality and performance of the six trapping schemes in terms of four key aspects: simplicity, robustness, flexibility, and efficiency. One of the schemes is novel: we introduce a simple, high quality scheme using a confocal design in which one trapping beam is effectively converted to two counter-propagating beams. The versatility of this new trapping scheme is demonstrated via application of the scheme to cavity ringdown spectroscopy. We hope this exploration of the diversity of PPF trapping schemes will extend applications of OT by providing researchers with information to assist in the selection of specific optical trapping schemes from the first-of-its-kind list of 21 configurations presented herein.

Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles.

Tryptophan is a fluorescent amino acid common in proteins. Its absorption is largest for wavelengths λ ≲ 290 nm and its fluorescence emissions peak around 300-350 nm, depending upon the local environment. Here we report the observation of red fluorescence near 600 nm emerging from 488-nm continuous-wave (CW) laser photoexcitation of dry tryptophan (Trp) particles. With an excitation intensity below 0.5 kW/cm2, dry Trp particles yield distinctive Raman scattering peaks in the presence of relatively weak and spectrally broad emissions with λ ∼500-700 nm, allowing estimation of particle temperature at low excitation intensities. When the photoexcitation intensity is increased to 1 kW/cm2 or more for a few minutes, fluorescence intensity dramatically increases by more than two orders of magnitude. The fluorescence continues to increase in intensity and gradually shift to the red when photoexcitation intensity and the duration of exposure are increased. The resulting products absorb at visible wavelengths and generate red fluorescence with λ ∼ 650-800 nm with 633-nm CW laser excitation. We attribute the emergence of orange and red fluorescence in the Trp products to a photochemical transformation that is instigated by weak optical transitions to triplet states in Trp with 488-nm excitation and which may be expedited by a photothermal effect.

Raman Spectroscopy of Optically Trapped Single Biological Micro-Particles.

The combination of optical trapping with Raman spectroscopy provides a powerful method for the study, characterization, and identification of biological micro-particles. In essence, optical trapping helps to overcome the limitation imposed by the relative inefficiency of the Raman scattering process. This allows Raman spectroscopy to be applied to individual biological particles in air and in liquid, providing the potential for particle identification with high specificity, longitudinal studies of changes in particle composition, and characterization of the heterogeneity of individual particles in a population. In this review, we introduce the techniques used to integrate Raman spectroscopy with optical trapping in order to study individual biological particles in liquid and air. We then provide an overview of some of the most promising applications of this technique, highlighting the unique types of measurements enabled by the combination of Raman spectroscopy with optical trapping. Finally, we present a brief discussion of future research directions in the field.

Optical trap for both transparent and absorbing particles in air using a single shaped laser beam.

Optical trapping of airborne particles is emerging as an essential tool in applications ranging from online characterization of living cells and aerosols to particle transport and delivery. However, existing optical trapping techniques using a single laser beam can trap only transparent particles (via the radiative pressure force) or absorbing particles (via the photophoretic force), but not particles of either type-limiting the utility of trapping-enabled aerosol characterization techniques. Here, we present the first optical trapping technique capable of trapping both transparent and absorbing particles with arbitrary morphology using a single shaped laser beam. Such a general-purpose optical trapping mechanism could enable new applications such as trapping-enabled aerosol characterization with high specificity.

Photophoretic trapping of airborne particles using ultraviolet illumination.

We demonstrate photophoretic trapping of micron-sized absorbing particles in air using pulsed and continuous-wave (CW) ultraviolet laser illumination at wavelengths of 351 nm and 244 nm. We compared the particle trapping dynamics in two trapping geometries consisting of a hollow optical cone formed by light propagating either with or against gravity. This comparison allowed us to isolate the influence of the photophoretic force from the radiative pressure and the convective forces. We found that the absorbing spherical particles tested experienced a positive photophoretic force, whereas the spatially irregular, non-spherical particles tested experienced a negative photophoretic force. By using two trapping geometries, both spherical and non-spherical absorbing particles could be trapped and held securely in place. The position of the trapped particles exhibited a standard deviation of less than 1 µm over 20 seconds. Moreover, by operating in the UV and deep-UV where the majority of airborne materials are absorptive, the system was able to trap a wide range of particle types. Such a general purpose optical trap could enable on-line characterization of airborne particles when coupled with interrogation techniques such as Raman spectroscopy.

Polarization-resolved near-backscattering of airborne aggregates composed of different primary particles.

We measured the polarization-resolved angular elastic scattering intensity distribution of aggregates composed of primary particles with different shapes and packing densities in the near-backward directions (155°-180°). Specifically, we compare aggregates composed of spherical polystyrene latex spheres, cylinder-like Bacillus subtilis particles, and Arizona road dust, as well as tryptophan particles. We observe clearly differentiable polarization aspect ratios and find that the negative polarization dip is more pronounced in more densely packed aggregates or particles. This work indicates that the polarization aspect ratio in the near-backward direction may be used as a fingerprint to discriminate between aggregates with the same size and overall shape by differences in their constituent particles.