Engineering topics
Kanik, Isik
Publications and source records attributed to Kanik, Isik.
Differential Mobility Spectrometer with Spatial Ion Detector and Methods Related Thereto
Differential mobility spectrometer with spatial ion detector and methods related thereto are disclosed. The use of one or more spatial detector within differential mobility spectrometry can provide for the identification and separation of ions with similar mobility and mass.
Improved Ambient Pressure Pyroelectric Ion Source
The detection of volatile vapors of unknown species in a complex field environment is required in many different applications. Mass spectroscopic techniques require subsystems including an ionization unit and sample transport mechanism. All of these subsystems must have low mass, small volume, low power, and be rugged. A volatile molecular detector, an ambient pressure pyroelectric ion source (APPIS) that met these requirements, was recently reported by Caltech researchers to be used in in situ environments.
Automated Desalting Apparatus
Because salt and metals can mask the signature of a variety of organic molecules (like amino acids) in any given sample, an automated system to purify complex field samples has been created for the analytical techniques of electrospray ionization/ mass spectroscopy (ESI/MS), capillary electrophoresis (CE), and biological assays where unique identification requires at least some processing of complex samples. This development allows for automated sample preparation in the laboratory and analysis of complex samples in the field with multiple types of analytical instruments. Rather than using tedious, exacting protocols for desalting samples by hand, this innovation, called the Automated Sample Processing System (ASPS), takes analytes that have been extracted through high-temperature solvent extraction and introduces them into the desalting column. After 20 minutes, the eluent is produced. This clear liquid can then be directly analyzed by the techniques listed above. The current apparatus including the computer and power supplies is sturdy, has an approximate mass of 10 kg, and a volume of about 20 20 20 cm, and is undergoing further miniaturization. This system currently targets amino acids. For these molecules, a slurry of 1 g cation exchange resin in deionized water is packed into a column of the apparatus. Initial generation of the resin is done by flowing sequentially 2.3 bed volumes of 2N NaOH and 2N HCl (1 mL each) to rinse the resin, followed by .5 mL of deionized water. This makes the pH of the resin near neutral, and eliminates cross sample contamination. Afterward, 2.3 mL of extracted sample is then loaded into the column onto the top of the resin bed. Because the column is packed tightly, the sample can be applied without disturbing the resin bed. This is a vital step needed to ensure that the analytes adhere to the resin. After the sample is drained, oxalic acid (1 mL, pH 1.6-1.8, adjusted with NH4OH) is pumped into the column. Oxalic acid works as a chelating reagent to bring out metal ions, such as calcium and iron, which would otherwise interfere with amino acid analysis. After oxalic acid, 1 mL 0.01 N HCl and 1 mL deionized water is used to sequentially rinse the resin. Finally, the amino acids attached to the resin, and the analytes are eluted using 2.5 M NH4OH (1 mL), and the NH4OH eluent is collected in a vial for analysis.
High-Voltage, Asymmetric-Waveform Generator
The shapes of waveforms generated by commercially available analytical separation devices, such as some types of mass spectrometers and differential mobility spectrometers are, in general, inadequate and result in resolution degradation in output spectra. A waveform generator was designed that would be able to circumvent these shortcomings. It is capable of generating an asymmetric waveform, having a peak amplitude as large as 2 kV and frequency of several megahertz, which can be applied to a capacitive load. In the original intended application, the capacitive load would consist of the drift plates in a differential-mobility spectrometer. The main advantage to be gained by developing the proposed generator is that the shape of the waveform is made nearly optimum for various analytical devices requiring asymmetric-waveform such as differential-mobility spectrometers. In addition, this waveform generator could easily be adjusted to modify the waveform in accordance with changed operational requirements for differential-mobility spectrometers. The capacitive nature of the load is an important consideration in the design of the proposed waveform generator. For example, the design provision for shaping the output waveform is based partly on the principle that (1) the potential (V) on a capacitor is given by V=q/C, where C is the capacitance and q is the charge stored in the capacitor; and, hence (2) the rate of increase or decrease of the potential is similarly proportional to the charging or discharging current. The proposed waveform generator would comprise four functional blocks: a sine-wave generator, a buffer, a voltage shifter, and a high-voltage switch (see Figure 1). The sine-wave generator would include a pair of operational amplifiers in a feedback configuration, the parameters of which would be chosen to obtain a sinusoidal timing signal of the desired frequency. The buffer would introduce a slight delay (approximately equal to 20 ns) but would otherwise leave the fundamental timing signal unchanged. The buffered timing signal would be fed as input to the level shifter. The output of the level shifter would serve as a timing and control signal for the high-voltage switch, causing the switch to alternately be (1) opened, allowing the capacitive load to be charged from a high-voltage DC power supply; then (2) closed to discharge the capacitive load to ground. Hence, the output waveform would closely approximate a series of exponential charging and discharging curves (see Figure 2).
Experimental and Coupled-channels Investigation of the Radiative Properties of the N2 c4 (sup 1)Sigma+(sub u) - X (sup 1)Sigma+(sub g) Band System
The emission properties of the N2 c(sup prime)(sub 4) (sup 1)Sigma+(sub u) - Chi (sup 1)Sigma+(sub g) band system have been investigated in a joint experimental and coupled-channels theoretical study. Relative intensities of the c(sup prime)(sub 4) (sup 1)Sigma+(sub u)(0) - Chi (sup 1)Sigma+(sub g)(v(sub i)) transitions, measured via electron-impact-induced emission spectroscopy, are combined with a coupled-channel Schroedinger equation (CSE) model of the N2 molecule, enabling determination of the diabatic electronic transition moment for the c(sup prime)(sub 4) (sup 1)Sigma+(sub u) - Chi (sup 1)Sigma+(sub g) system as a function of internuclear distance. The CSE probabilities are further verified by comparison with a high-resolution experimental spectrum. Spontaneous transition probabilities of the c(sup prime)(sub 4) (sup 1)Sigma+(sub u) - Chi (sup 1)Sigma+(sub g) modeling atmospheric emission, can now be calculated reliably.
Utilizing Ion-Mobility Data to Estimate Molecular Masses
A method is being developed for utilizing readings of an ion-mobility spectrometer (IMS) to estimate molecular masses of ions that have passed through the spectrometer. The method involves the use of (1) some feature-based descriptors of structures of molecules of interest and (2) reduced ion mobilities calculated from IMS readings as inputs to (3) a neural network. This development is part of a larger effort to enable the use of IMSs as relatively inexpensive, robust, lightweight instruments to identify, via molecular masses, individual compounds or groups of compounds (especially organic compounds) that may be present in specific environments or samples. Potential applications include detection of organic molecules as signs of life on remote planets, modeling and detection of biochemicals of interest in the pharmaceutical and agricultural industries, and detection of chemical and biological hazards in industrial, homeland-security, and industrial settings.
Miniature Focusing Time-of-Flight Mass Spectrometer
An improved miniature time-of-flight mass spectrometer has been developed in a continuing effort to minimize the sizes, weights, power demands, and costs of mass spectrometers for such diverse applications as measurement of concentrations of pollutants in the atmosphere, detecting poisonous gases in mines, and analyzing exhaust gases of automobiles. Advantageous characteristics of this mass spectrometer include the following: It is simple and rugged. Relative to prior mass spectrometers, it is inexpensive to build. There is no need for precise alignment of its components. Its mass range is practically unlimited Relative to prior mass spectrometers, it offers high sensitivity (ability to measure relative concentrations as small as parts per billion). Its resolution is one dalton (one atomic mass unit). An entire mass spectrum is recorded in a single pulse. (In a conventional mass spectrometer, a spectrum is recorded mass by mass.) The data-acquisition process takes only seconds. It is a lightweight, low-power, portable instrument. Although time-of-flight mass spectrometers (TOF-MSs) have been miniaturized previously, their performances have not been completely satisfactory. An inherent adverse effect of miniaturization of a TOF-MS is a loss of resolution caused by reduction of the length of its flight tube. In the present improved TOF-MS, the adverse effect of shortening the flight tube is counteracted by (1) using charged-particle optics to constrain ion trajectories to the flight-tube axis while (2) reducing ion velocities to increase ion flight times. In the present improved TOF-MS, a stream of gas is generated by use of a hypodermic needle. The stream of gas is crossed by an energy-selected, pulsed beam of electrons (see Figure 1). The ions generated by impingement of the electrons on the gas atoms are then focused by three cylindrical electrostatic lenses, which constitute a segmented flight tube. After traveling along the flight tube, the ions enter a charged-particle detector. The output of the detector is fed to a counting circuit to obtain data on the counting rate as a function of time. Inasmuch as time of flight is directly proportional to the ion mass, a plot of the counting rate versus time of flight is equivalent to a mass spectrum (see Figure 2).
Proton-transfer-reaction/ion-mobility-spectrometer and method of using the same
A high-pressure hollow cathode ionizer is combined with an ion-mobility-spectrometer (IMS) for the detection of trace amounts of organic compounds in gas. The ionizer uses H.sub.3 0.sup.+, ions which do not react with air to ionize the organic compounds and the organic compounds are soft ionized. The ionized organic compounds are detected in the IMS at levels of parts per billion and identified using calibrated reference tables. Applications include but are not limited to the fields of: (1) medicine as a breath analyzer for detection of lung cancer, diabetes, liver cirrhosis, (2) law enforcement in drug interdiction and explosives detection, (3) food monitoring and control, (4) environmental monitoring and (5) space applications.
A high pressure hollow cathode ionization source for in-situ detection of organic molecules on Mars
We have designed, constructed and characterized a new high-pressure (1-5 Torr) hollow cathode discharge source (HCDSj that can be utilized as an ionizer in a wide variety of mass analyzers. It is able to function under ambient Martian atmospheric conditions without modification.
High-Resolution Studies of Extreme-Ultraviolet Emission from CO by Electron Impact
We report a high-resolution study (0.0036 nm full width at half maximum) of electron-impact-induced emission spectra of CO at 30-, 75-, and 100-eV electron-impact energies. The spectral features were acquired in optically thin conditions. At the specified resolution, attainable with our 3-m vacuum ultraviolet spectrometer, we observe rotationally resolved emission bands of CO in the extreme ultraviolet, from the vibronic states B (sup 1)sigma(sup +)(0), C (sup 1)sigma(sup+)(0), and E (sup 1)pi(0), to the ground state X (sup 1)sigma(sup +)(0). A simple model of these bands, based on the Honl-London factors and the rotational constants, is constructed and is shown to be in good agreement with the observed spectra. The predissociation yield for the E (sup 1)pi electronic state has been determined, showing that the E state has the largest predissociation cross section of CO for all singlet-state Rydberg series members. The excitation function of the [E (sup 1)pi(0) yields X (sup 1)sigma(sup +)(0)] transition, in the 0-800-eV impact energy range, is measured, permitting determination of the oscillator strength by using a modified Born approximation analytical fit.
High-Resolution Studies of Extreme-Ultraviolet Emission from CO by Electron Impact
We report a high-resolution study [0.0036 nm full width at half maximum (FWHM) of electron-impact-induced emission spectra of CO 1t 30, 75 and 100 eV electron-impact energies. The spectral features were acquired in optically thin conditions, and represent the highest resolution single-scattering emission spectrum of CO induced by electron impact yet available.
Far-Ultraviolet Emission Cross Sections of Ne 2 and Ne 3 Excited by Electron Impact
We have measured the electron-impact-induced fluorescence spectrum of neon in the wavelength range 120-270 nm at a spectral resolution of 0.43 nm (FWHM). The strongest lines observed in the far-ultraviolet (FUV) spectrum of neon are assigned to terms of the doublet system of Ne 2 (2s(sup 2) 2p(sup 4)nl and the triplet system of Ne 3 (2s(sup 2)2p(sup 3)3l). Our FUV spectral data, obtained at 300 eV electron-impact energy, provide absolute emission cross sections of these Ne 2 and Ne 3 lines, and are compared to previous measurements where available. In addition, the excitation function of the strongest Ne II line observed at 191.6 nm was measured from threshold to 1000 eV electron-impact energy.
Kinetic Energy Distribution of H(2p) Atoms from Dissociative Excitation of H2
The kinetic energy distribution of H(2p) atoms resulting from electron impact dissociation of H2 has been measured for the first time with uv spectroscopy. A high resolution uv spectrometer was used for the measurement of the H Lyman-alpha emission line profiles at 20 and 100 eV electron impact energies. Analysis of the deconvolved 100 eV line profile reveals the existence of a narrow line peak and a broad pedestal base. Slow H(2p) atoms with peak energy near 80 meV produce the peak profile, which is nearly independent of impact energy. The wings of H Lyman-alpha arise from dissociative excitation of a series of doubly excited Q(sub 1) and Q(sub 2) states, which define the core orbitals. The fast atom energy distribution peaks at 4 eV.
Medium-resolution studies of extreme-ultraviolet emission from CO by electron impact
We report medium-resolution (0.025 nm full width at half maximum (FWHM)) electron impact-induced emission spectra of CO for 20, 100, and 200 eV impact energies. The emission spectra correspond to the extreme ultraviolet transitions from the B (sup 1)Sigma(sup +)(0), and E (sup 1)Pi(0) vibronic states to the X (sup 1)Sigma(sup +)(0) ground state. The present measurements are carried out at 20 times higher spectral resolution (to separate the many blended components) compared to our previous measurements, which were at a spectral resolution of 0.5 nm FWHM. The emission cross sections corresponding to the B (sup 1)Sigma(sup +)(0) yields X (sup 1)Sigma(sup +)(0), C (sup 1)Sigma(sup +)(0) yields X (sup 1)Sigma(sup +)(0), and E (sup 1)Pi(0) yields X (sup 1)Sigma(sup +)(0) resonance transitions were measured. In addition, excitation functions (0-1 keV) extending well into the Born region have been measured for the strong transitions (B (sup 1)Sigma(sup +)(0) yields X (sup 1)Sigma(sup +)(0) and C (sup 1)Sigma(sup +)(0)) and oscillator strengths have been determined, using a modified Born approximation analytic fit to the measured excitation function.
Hubble Space Telescope UV spectral observations of Io passing into eclipse
Time-resolved spectra of Io have been obtained with the Faint Object Spectrograph on the Hubble Space Telescope in January 1992 at times centered on the passage of Io into Jupiter's shadow. Two different eclipse observations covered 1100-1600 A and 2250-3300 A. In the far ultraviolet(far-UV) range, emission lines of atomic sulfur and oxygen from Io's atmosphere (similar to those previously detected with the International Ultraviolet Explorer (IUE)) have been observed from Io in sunlight, and the spatial extent of the emitting region has been resolved for the first time: this is 0.5-1 Io radii (R(sub Io)) above the surface. The emission lines are typically 1kR in brightness while Io is in sunlight, and decrease to a few hundred Rayleighs within 20 min or less of Io's passing into shadow. If the emissions are produced in Io's ionosphere, the decrease in shadow appears consistent with the collisional slowing and recombination of photoelectrons in 100-1000 s, with recombination an important quenching process if the dominant ion is molecular (i.e., SO2(+)) condensation, with the residual emission in shadow due either to plasma impact of gas above the hot volcanic calderas or electron impact on S and O. In the near-UV range, we have not detected any airglow emissions from Io's atmosphere in shadow, with the main limitation being a high level of scattered light from Jupiter. We derive a 3 sigma upper limit to the 2560 A SO emission feature of 1 KR, which is close to what is expected from electron impact on SO2 based on the obs erved brightness of the FUV S and O lines in shadow. A high signal-to-noise spectrum of Io's albedo in sunlight reveals a spectral shape similar to laboratory spectra of SO2 frost reflectivity, and the relative albedo spectrum changed as Io passed into eclipse and part of the disk was in shadow. No specific SO2 gas absorption features appear in the albedo spectrum, although there could be substantial gas absorption near 2800 A if the individual lines are narrow and saturated. Finally, we present preliminary models for the near-UV spectrum of Io as functions of SO2 frost areal coverage and SO2 gas density.
The complete UV spectrum of SO2 by electron impact. I - The vacuum ultraviolet spectrum
Measurements of the VUV emission cross sections of SO2 from 40 to 200 nm in the laboratory in a crossed beam experiment are reported. The wavelength range comprised the EUV spectrum, from 40 to 120 nm, and the FUV spectrum, from 120 to 200 nm. The studies included the measurement of excitation functions of the strongest multiplets from 0 to 1 keV impact energy and the identification of dissociation processes from the analysis of the threshold excitation function. It is shown that the FUV emission cross sections for dissociative excitation of atomic multiplets are generally much larger in the FUV than in the EUV. The emission cross sections measured are important for the preparation and data analysis of spacecraft observations of Io to be obtained for the 1990s.