Planar geometry for trapping and separating ions and charged particles.

A planar quadrupole ion trap is proposed. We have demonstrated an extremely large operating range by trapping ions and particles with mass-to-charge ratio ranging from 10(2) to 10(9) at frequencies from 2.8 x 10(6) to 60 Hz at an operating pressure of 1.1 x 10(-4) to 760 Torr, respectively, using a trap radius of r1 = 1 mm. We have also performed mass spectrometry with a resolution of 1.2 amu with mass-to-charge range from 50 to 150. Our geometry is simple enough to be integrated into existing integrated circuits and microelectromechanical system devices, opening up the possibility of many novel hybrid applications and experiments.

Microfabricated quadrupole ion trap for mass spectrometer applications.

An array of miniaturized cylindrical quadrupole ion traps, with a radius of 20 microm, is fabricated using silicon micromachining using phosphorus doped polysilicon and silicon dioxide for the purpose of creating a mass spectrometer on a chip. We have operated the array for mass-selective ion ejection and mass analysis using Xe ions at a pressure of 10(-4). The scaling rules for the ion trap in relation to operating pressure, voltage, and frequency are examined.

Pulsed-ionization miniature ion mobility spectrometer.

We have demonstrated a miniature ion mobility spectrometer (IMS) that employs single pulses of corona discharge ionization. IMS spectra of both positive and negative ions generated from ambient air were measured as a function of drift field under various ionization conditions. Ion mobility spectra were studied with various pulse widths for both positive and negative ions, giving insights into mechanisms and kinetics of corona discharge ionization used in the miniature IMS. A combination of a pulsed potential with a steady dc bias was used to generate ions in the miniature IMS. There was a threshold dc potential for ion generation for a given pulse height. The dc ionization threshold was found to decrease linearly with increasing pulse height.

Laser desorption/ionization coupled to tandem mass spectrometry for real-time monitoring of paraquat on the surface of environmental particles.

Aerosol mass spectrometry with laser desorption/ionization was investigated as a possible tool for real-time monitoring of the presence of the pesticide paraquat on the surface of airborne soil particles. Laser desorption/ionization of paraquat dication produced only singly charged ions. The most abundant species were [M](+.), [M - H](+), and [M - CH3](+). Operation of the ion trap mass spectrometer in the MS(3) mode allowed the reduction of the signal dependence on laser fluence fluctuations and permitted the detection of the analyte with good sensitivity and high selectivity. The estimated limit of detection in terms of surface coverage was 0.016 monolayers, approximately 1 attomole of paraquat on the surface of a single micron-sized soil particle.

Laser desorption/in situ chemical ionization aerosol mass spectrometry for monitoring tributyl phosphate on the surface of environmental particles.

The possibility of using real-time aerosol mass spectrometry (RTAMS) for the detection of surface-adsorbed tributyl phosphate (TBP) as an alkali metal adduct has been investigated. Environmental particles contain variable amounts of easily ionizable alkali metals. During laser desorption of surface-adsorbed TBP molecules, Na+ and K+ ions are generated by the interaction of the laser radiation with the particle's material. The alkali metal ions serve as in situ chemical ionization reagents of the neutral analyte molecules. The effect of laser fluence on the signal intensities of the potassium ion and cationized TBP was also studied. The best performance of the instrument was observed with laser fluences that produce high abundances of K+ but low abundances of ions from the particle's bulk material. The relatively low laser fluence, necessary to produce potassium ions, prevents the excessive fragmentation of the analyte. The instrument is capable of real-time monitoring of submonolayer coverage of TBP on the surface of micron-sized particles.

Space charge effects on resolution in a miniature ion mobility spectrometer.

Miniaturization of ion mobility spectrometry (IMS) is expected to have many advantages, as well as difficulties, in the separation of chemical species at atmospheric pressure. We report the results of studies of a miniature ion mobility spectrometer that has a drift channel 1.7 mm in diameter, the smallest cross section reported to date. The miniature cell contains a homogeneous drift field and is operated at atmospheric pressure. The miniature IMS has been characterized by measuring both negative and positive ion spectra using a frequency-quadrupled Nd: YAG laser on samples of NO, O2, and methyl iodide; a useful resolution (> 10) was achieved with an operating voltage of 500 V. Peak broadening due to Coulomb repulsion was determined to have a major effect on the resolution of the miniature device.

Single-molecule analysis of ultradilute solutions with guided streams of 1--microm water droplets.

We describe instrumentation for real-time detection of single-molecule fluorescence in guided streams of 1-microm (nominal) water droplets. In this technique, target molecules were confined to droplets whose volumes were comparable with illumination volumes in diffraction-limited fluorescence microscopy and guided to the waist of a cw probe laser with an electrostatic potential. Concentration detection limits for Rhodamine 6G in water were determined to be approximately 1 fM, roughly 3 orders of magnitude lower than corresponding limits determined recently with diffraction-limited microscopy techniques for a chemical separation of similar dyes. In addition to its utility as a vehicle for probing single molecules, instrumentation for producing and focusing stable streams of 1-2-microm-diameter droplets may have other important analytical applications as well.

Spatial photoselection of single molecules on the surface of spherical microcavities.

We show that ultrasensitive microdroplet-stream fluorescence techniques combined with surfactant forms of Rhodamine dyes can be used to probe single molecules on the surfaces of spherical microcavities. Individual octadecyl Rhodamine B molecules, shown previously by ensemble measurements to be localized and oriented at the surfaces of liquid microspheres, were spatially photoselected primarily along great circles lying perpendicular or parallel to the detection axis by use of polarized laser excitation. A polarization dependence is observed in the distribution of single-molecule fluorescence amplitudes that can be interpreted qualitatively in terms of position-dependent fluorescence-collection efficiencies.

Time-domain observation of optical pulse propagation in whispering-gallery modes of glass spheres.

We report picosecond time-resolved measurements of optical pulse propagation in dielectric spheres (8, 10, and 26 mm in diameter) for which the pulse duration ( approximately 2 ps) was short compared with the equatorial round-trip time within the sphere. A size-independent buildup of the leakage intensity in terms of the number of round trips was observed for each of the spheres, as were damped low-frequency oscillations superimposed upon the pulse ringdown envelope. These features of the data are interpreted as resulting from perturbative coupling of eigenmodes of the sphere and trajectory precession near the observation region.

Tandem mass spectrometry of uranium and uranium oxides in airborne particulates.

A method for detection of uranium in airborne microparticles in real time has been developed. Positive identification of uranium is achieved by isolating UO(2+) ions and following their reaction with residual oxygen molecules to yield UO(2)(+).

Confinement and manipulation of individual molecules in attoliter volumes.

We report observation of fluorescence from individual rhodamine 6G molecules in streams of charged 1-µm-diameter water droplets. With this approach, illumination volumes comparable to diffraction-limited fluorescence microscopy techniques (≤500 aL) are achieved, resulting in similarly high contrast between single-molecule fluorescence signals and nonfluorescent background. However, since the fluorescent molecules are confined to electrically charged droplets, in situ electrodynamic manipulation (e.g., focusing, switching, or merging) can be accomplished in a straightforward manner, allowing experimental control over both the delivery of molecules of interest to the observation region and the laser-molecule interaction time. As illustrated by photocount statistics that are independent of molecular diffusion and spatial characteristics of the excitation field, individual rhodamine 6G molecules in 1-µm droplets are reproducibly delivered to a target a few micrometers in diameter at a rate of between 10 and 100 Hz, with laser beam transit times more than 1 order of magnitude longer than diffusion-limited laser-molecule interaction times in equivalent volumes of free solution.

Real-time observation of single-molecule fluorescence in microdroplet streams.

We report real-time observation of fluorescence bursts from individual Rhodamine 6G molecules in streams of microdroplets (peak signal-to-noise ratios, approximately 30) whose trajectories are constrained with a linear electric quadrupole. This approach offers a reasonable dynamic range in droplet size (3- 12-microm diameter) with <1% shot-to-shot size fluctuations and sensitivity comparable with that of droplet levitation techniques with at least 10(3) higher analysis rates. Applications to the study of single-molecule microcavity effects and stimulated emission are discussed.

Collection of fluorescence from single molecules in microspheres: effects of illumination geometry.

The collection of fluorescence from a molecule inside a sphere illuminated with single or counterpropagating plane waves is modeled. The results are applicable to microdroplet-based single molecule detection techniques and to some microparticle characterization techniques using inelastic emission. The large position-dependent variations in the fluorescence collection rate are primarily attributable to variations in the excitation intensity. With plane-wave illumination the collection from shadow regions is low because the incident energy is refracted by the droplet surface away from these regions. The average collection rate from molecules in shadow regions can be increased by illuminating with counterpropagating beams.

High-efficiency molecular counting in solution: single-molecule detection in electrodynamically focused microdroplet streams.

We report fluorescence detection of individual rhodamine 6G molecules using a linear quadrupole to focus streams of microdroplets through the waist of a counterpropagating cw Ar(+) laser. Since the terminal velocity scales as the square of the droplet diameter, the droplet-laser interaction time was "tunable" between 5 and 200 ms by using water samples spiked with a small, variable (2-5% v/v) amount of glycerol. Fluorescence bursts from droplets containing single molecules were clearly distinguished from the blanks in real time with an average signal-to-noise ratio of about 10, limited primarily by photobleaching and droplet size fluctuations (<1%). The volume throughput rates associated with this approach (∼10 pL/s) are roughly 10(3) higher than those associated with particle levitation techniques, with minimal sacrifice in sensitivity. Total molecular detection efficiencies of about 80% (at >99% confidence) were obtained for 100 and 15 fM rhodamine 6G solutions, in good agreement with detailed theoretical calculations and statistical limitations.

Modeling fluorescence collection from single molecules in microspheres: effects of position, orientation, and frequency.

We present calculations of fluorescence from single molecules (modeled as damped oscillating dipoles) inside a dielectric sphere. For an excited molecule at an arbitrary position within the sphere we calculate the fluorescence intensity collected by an objective in some well-defined detection geometry. We find that, for the cases we model, integration over the emission linewidth of the molecule is essential for obtaining representative results. Effects such as dipole position and orientation, numerical aperture of the collection objective, sphere size, emission wavelength, and linewidth are examined. These results are applicable to single-molecule detection techniques employing microdroplets.

Morphological resonances for multicomponent immunoassays.

An immunoassay technique capable of detecting and identifying a number of species of microorganisms in a single analysis is described. The method uses optical-resonance size discrimination of microspheres to identify antibodies to which stained microorganisms are bound.

Room-temperature microparticle-based persistent spectral hole burning memory.

We show both theoretically and experimentally that a random distribution of spherical microparticles may be used as a spectral hole burning memory. This microparticle hole burning memory, which can be both written and read at room temperature, is a direct consequence of the properties of morphology-dependent resonances of microparticles.

Mode selection in a continuous-wave dye laser with an intracavity photorefractive element.

Strong mode selection and frequency scanning have been observed for a cw dye laser with an intracavity BaTiO(3) crystal. Linewidths as low as 50 MHz have been achieved for certain positions of the crystal within the laser cavity.

Controlled scanning of a continuous-wave dye laser with an intracavity photorefractive element.

An intracavity photorefractive crystal is used in a cw dye laser. The frequency selection of the grating written in the crystal by the laser's standing-wave intensity pattern reduces the laser spectrum to a pair of hole-burning modes. The wavelength can be tuned by varying the laser-cavity length. Wavelength scans across an entire gain curve are possible without mode hops.

Phase-conjugate feedback into a continuous-wave ring dye laser.

Optical feedback from a BaTiO(3) passive phase-conjugate reflector into an untuned cw ring dye laser can narrow the linewidth to 1.3 GHz. Self-scanning effects are also observed. The linewidth results are interpreted in terms of spatial hole burning and longitudinal-mode competition.