An ultrashort-duration, high-repetition-rate pulse source for laser ionization/mass spectrometry.

This paper describes a sample inlet system with several advantages over other pulsed valves, as applied to resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry. The nozzle is based on online concentration by analyte adsorption/laser desorption (online COLD), where a capillary column with a narrowly synthesized tip is employed for sample introduction. The analyte molecules adsorbed at the tip are desorbed by a pulsed laser and are injected into a mass spectrometer as a packet. The online COLD nozzle can produce very short gas pulses on the order of 1 µs. Moreover, this nozzle is capable of operating over a wide range of repetition rates from 1 Hz to 1 kHz. In addition, this nozzle intrinsically possesses several unique characteristics; for instance, it can be heated to very high temperatures and has nearly zero dead volume. Therefore, the present sample introduction technique offers an ideal and versatile nozzle for laser ionization/mass spectrometry.

A pair of concentric capillaries as an interface for gas chromatography and supersonic jet/multiphoton ionization/mass spectrometry.

A pair of concentric capillaries was developed to mix helium, which was used as the carrier gas for gas chromatography, with argon for efficient molecular cooling by supersonic jet expansion. A simple instrument was constructed for the evaluation of nozzle diameter using the Hagen-Poiseuille equation. The effects of nozzle diameter, type of expansion gas, flow rate, and the distance from the nozzle to the observation region were investigated. Mixing argon gas with the carrier gas helium resulted in efficient molecular cooling from 30 to 10 K and the complete disappearance of the background signal from the multiphoton ionization spectrum. Consequently, the spectral selectivity was significantly improved and the nozzle was successfully applied to isomer-selective analysis of dichlorotoluenes. Since the dead volume in the nozzle was negligible, it was suitable as an interface for gas chromatography and supersonic jet/multiphoton ionization/mass spectrometry.

Residual formaldehyde on plastic materials and medical equipment following low-temperature steam and formaldehyde sterilization.

We measured the amount of residual formaldehyde on 16 plastic materials and five medical devices following low-temperature steam and formaldehyde (LTSF) sterilization, based on the European Standard EN14180. The amounts of formaldehyde residue on the plastic materials were compared with that on a filter paper of similar dimensions. The amount of residual formaldehyde on polyamide 6, polyurethane, natural rubber and polyacetal was higher (21.9, 15.2, 3.0 and 2.1 times, respectively) than that on the filter paper. The amount of formaldehyde recovered from a breathing circuit, anaesthesia circuit, oxygen tubing, airway tube and tweezers was 260, 240, 594, 56 and 0 microg, respectively, following LTSF sterilization. Our results emphasize the need to verify the main material composing the medical equipment before LTSF sterilization, as the amount of formaldehyde retrieved following sterilization varies according to the material used for construction.

Evaluation of a low-temperature steam and formaldehyde sterilizer.

We evaluated a low-temperature steam and formaldehyde (LTSF) sterilizer based on the draft European Standard prEN 14180. Microbiological tests were conducted on small and full loads using process challenge devices in five programs (P1-P5). With small loads all tests showed no growth of Bacillus stearothermophilus (ATCC7953) spores. However, positive cultures were observed with full-load tests using P5 (sterilization temperature, 50 degrees C). Our data indicated that the load influenced the efficacy of the LTSF sterilizer. Desorption tests were conducted to determine residual formaldehyde in indicator strips. The mean concentrations of formaldehyde in P1-P5 were 31.9, 56.3, 54.9, 82.2 and 180.6 microg, respectively, which are below the limits allowed by the draft Standard. Our results indicate that the LTSF sterilizer is useful for sterilization because of its excellent efficacy, short handling time, and safety.

Generation of highly repetitive optical pulses based on intracavity four-wave Raman mixing.

An extremely long train of highly repetitive pulse (17 THz) is obtained by the rotational four-wave Raman mixing of molecular hydrogen in a resonator using a computer simulation. This highly repetitive pulse can be obtained only when the laser wavelength and the resonator are adjusted to specified values. This pulse train has potential for use in ultrafast data communication because of the accurately determined repetition rate or even as a frequency standard, since the frequencies of the emission lines can be stabilized and locked to the above values.

Development of tunable picosecond dye laser for multiphoton ionization of dioxin precursors in supersonic jet/time-of-flight mass spectrometry.

A distributed-feedback dye laser has been developed for achieving the efficient multiphoton ionization of chlorobenzene and dichlorobenzene, that is, precursor molecules of dioxins. This tunable picosecond laser with a narrow spectral line width, that is, a nearly transform-limited pulse, provides a more efficient ionization than the nanosecond laser, which is currently in use in supersonic jet spectrometry. The advantage of picosecond over nanosecond and femtosecond lasers is also discussed on the basis of the theoretical model reported in a previous paper.

Immunoassay for human serum albumin using capillary electrophoresis-semiconductor laser-induced fluorometry.

Capillary electrophoresis combined with semiconductor laser-induced fluorometry was applied to an immunoassay of human serum albumin. Human serum albumin was labeled with a fluorescent molecule (Cy5), which has an absorption maximum at 649 nm. The labeled albumin was purified by ultrafiltration in order to reduce signals, which are unreacted labeling reagent, product, and fragment products derived there from. After the purification, no signal for unreacted labeling reagent and fragment products was detectable in the electropherogram of the labeled albumin. The labeled albumin was then reacted with anti-albumin to form an immunocomplex, which was separated from the excess free albumin. The competitive immunoassay was used in the determination of human serum albumin in a controlled serum sample, using the labeled albumin. The obtained value was found to be 0.21 +/- 0.02 mg/ml, which is in good agreement with other known values.

Characterization of phosphor materials for use in plasma display panel by time-resolved vacuum-ultraviolet laser spectrometry.

Phosphor materials that were manufactured for use in a plasma display panel (PDP) were investigated by employing a newly designed time-resolved vacuum-ultraviolet (VUV) spectrometer, which consists of a pulsed VUV laser and a fast photodetector. The VUV spectrometer was used to collect quantum efficiency data as well as the rise and decay times for the PDP phosphor luminescence. Both the rise and decay times increased with decreasing excitation wavelength in the VUV region. This result can be explained by a change in the mechanisms of photoexcitation and luminescence, that is, from charge-transfer excitation to host-lattice excitation below 200 nm. The present instrument was also used for an evaluation of the phosphor materials (Ba(1 - x)MgAl10O17:Eu2+(x)) by changing the Eu2+ concentration. The obtained data suggest that the impurities and defects are located inside the host crystal. Thus, the VUV spectrometer constructed in this study has considerable potential for use in investigating the nature of PDP phosphor materials.

An "optical channel": a technique for the evaluation of biological cell elasticity.

The development of an optical channel, a new analytical technique for evaluating the elasticity of biological cells, is described in this study. Two types of erythrocyte cells, i.e., young and old cells, were examined via their introduction into a flowing medium, to which a laser beam was focused in the opposite direction. An erythrocyte cell is trapped in a laser beam by a gradient force, moves in the downstream direction, and is then elongated at the beam waist. The change in shape was measured directly using a microscope equipped with a charge-coupled-device camera. It is probable the main driving force for the cell deformation is a shear stress generated by a medium flow, since an estimate of the gradient force suggests that it is too small to change the shape of an erythrocyte. The average values of the elongation of young and old cells were 2.4+/-0.6 and 2.1+/-0.5, respectively. These values are in reasonably good agreement with values obtained using a rheoscope method. The deformation was measured without any physical contact to the solid surface, and therefore, damage to cells such as these are minimal.

Determination of motility forces of bovine sperm cells using an "optical funnel".

An optical funnel, a new technique for the evaluation of the force of a microorganism, was applied to the determination of the motility force of bovine sperm cells. In this approach, sperm cells, suspended in an aqueous solution, are introduced into a flow cell, to which radiation pressure is applied from the direction opposite to a medium flow. The sperm cell, which is moving in a stream, is captured by radiation pressure and forced to move to the position at which the force induced by the laser radiation is equal to the force induced by a medium flow. The sperm cell then escapes by its own power on the way to this equilibrium (entrapping) position. The radiation force increases with decreasing distance from the focal point, and as a result, the force of the sperm cell can be determined by measuring the position where the sperm cell escaped against the laser irradiation field. The motility force of the sperm cell was measured in aqueous solution at different pH values and potassium ion concentrations. It was possible to measure more than 250 sperm cells in 3 h. Thus, the optical funnel has potential for use as a rapid and repetitive means for the determination of the motility force of the sperm cell.

Supersonic jet/multiphoton ionization/mass spectrometry of dioxins formed by the thermal reaction of phenols in the absence and presence of an FeCl3 catalyst.

Dioxins, which are thermally produced from several precursor molecules, were investigated by supersonic jet/multiphoton ionization/time-of-flight mass spectrometry (SSJ/MPI/TOF-MS). Dibenzofuran and dibenzo-p-dioxin were efficiently generated from o-chlorophenol and also from phenol after a chlorination reaction with FeCl3. The present technique was employed for the continuous monitoring of a specified isomer, e.g., m-chlorophenol, which is formed at relatively low temperatures by chlorination of phenol with FeCl3. A dimerization reaction that forms a dibenzo-p-dioxin, e.g., dichlorodibenzo-p-dioxin from 2,4-dichlorophenol, at relatively high temperatures was also investigated. The number of chlorine atoms in the dioxin molecule was largely correlated with the number of chlorine atoms in the precursor molecule. However, some unexpected compounds, which probably occur by dechlorination and rearrangement reactions, were also found. Thus, the SSJ/MPI/TOF-MS technique represents a sensitive, as well as selective, analytical method for monitoring thermally generated dioxins.

Analysis of thermal decomposition products arising from polyvinyl chloride analogs by supersonic jet/multiphoton ionization/mass spectrometry.

Polyvinyl chloride (PVC) and chlorinated polyvinyl chloride (CPVC) were thermally decomposed at 200-500 degrees C, and the reaction products measured by supersonic jet/multiphoton ionization/mass spectrometry. No precursor molecules of dioxins, such as chlorobenzene, were observed from PVC, although benzene was produced as one of the major components. On the other hand, a large peak corresponding to chlorobenzene was observed, when CPVC was used as a sample. These results suggest that the release of hydrogen chloride and aromatic ring formation occur efficiently and produce chlorinated aromatic hydrocarbons only when excess chlorine atoms are present in the chain of PVC. This method, which has very high selectivity is preferred for trace analysis of specific compounds such as dioxin precursors in a complex mixture. Isomer-selective analysis, e.g. detection of o-, m-, and p-dichlorobenzenes, is also demonstrated in this study.

Diode lasers in analytical chemistry.

In this review article, I report the structure and characteristics of a diode laser and the figure of merits in the application to analytical spectroscopy. This diode laser is currently used in absorption-based and fluorescence-based spectrometries. Due to their ultra-high detectability, single atoms and molecules can be detected in the extreme case. Moreover, selectivity is improved by time-resolved spectrometry and also by a combination with separation techniques such as chromatography. Second harmonic generation is employed to extend the laser wavelength, in order to expand the analytical application. Finally, limitations of the diode laser are pointed out, and the problem, which should be solved in the near future, is also described.

Optical chromatography Size determination by eluting particles.

A new method for the determination of particle size was developed using optical chromatography. After separating polystyrene particles, the laser power was gradually reduced, permitting the elution of small to large particles. Particle size was calculated from the laser power when the particle was eluted with a medium flow. This approach is more accurate than the technique previously reported because there is no need to determine the position of the beam waist. Advantages of the new approach are discussed theoretically and experimentally. The precision in size determination was improved by a factor of 3.3, i.e. the standard deviation in the measurement was reduced from 10 to 3% for 1 mum beads by replacing optical chromatography with the present method.

Hadamard transform capillary electrophoresis.

This paper reports the first demonstration of a multiplex sample injection technique in capillary electrophoresis. The sample was injected into a capillary (effective length, 4 cm) as a pseudorandam Hadamard sequence by a photodegradation technique using a high-power gating laser, and the fluorescence signal, which was measured using a probe excitation beam, was decoded by an inverse Hadamard transformation. The signal-to-noise ratio was improved by a factor of 8, which was in good agreement with the theoretically predicted value of 8.02. This approach is potentially useful for the enhancement of the sensitivity by 3 orders of magnitude in high-resolution capillary electrophoresis, combined with fluorescence detection.

Diffractive optical chemical sensor based on light absorption.

A new type of chemical sensor based on light absorption is proposed. An array of zones alternatively containing the pH indicator thymolphthalein is formed in a gelatin film. By changing the sample solution from acidic to alkaline, a blue stripe appears in the gelatin film. This acts as a transmission grating and diffracts the introduced laser beam. Theory predicts that this method, which is based on light absorption/beam diffraction, is as sensitive as or more sensitive than fluorometry.

Effect of laser pulse width on ionization efficiency in supersonic beam-multiphoton ionization-mass spectrometry.

The efficiency in multiphoton ionization is calculated for various molecules with different lifetimes, based on a kinetic model using rate equations. The results are strongly dependent on the types of resonance ionization, i.e., ionization through congested intermediate levels or ionization through a discrete intermediate level. In the former case, a laser pulse shorter than the lifetime is always preferred for efficient ionization. In the latter case, a 10-ps laser pulse provides the maximum ionization efficiency for a molecule with a lifetime in excess of 10 ps. For a molecule having a lifetime shorter than 10 ps, the use of a laser whose pulse width is adjusted to the same value as the lifetime is suggested. The results obtained by a computer simulation are in reasonably good agreement with the experimental data obtained for monohalogenated benzenes.

Application of optical chromatography to immunoassay.

Optical chromatography, a new separation technique involving the use of a radiation force and a medium flow, is used for trace analysis of protein. Two polystyrene beads, coated with antibody (anti-mouse IgG), are combined in the presence of an antigen (mouse IgG). The bound (B) and free (F) beads are readily separated by optical chromatography, and the B/F ratio can be correlated with the concentration of antigen (protein). Nanomolar concentrations of protein can be measured by this technique. The rates of the forward and reverse immunological reactions were independently determined by measuring the time of formation and dissociation, respectively, of the immunobeads.

Theory of optical chromatography.

To evaluate the performance of optical chromatography, a number of equations are theoretically derived using a ray-optics model. These mathematical formalisms are experimentally verified by determining the relationship between the velocity of motion of a polystyrene bead with respect to the intensity of an applied radiation force under the condition where there exists no applied fluid flow. The force is confirmed to be at a maximum at the focal point and to decrease with increasing distance from this position. The radiation force is verified to be proportional to the square of the particle size when the particle diameter is much smaller than the beam diameter. In addition, the radiation force is ascertained to be proportional to the laser power. These results are in excellent agreement with the proposed theoretical model, which is based on ray optics. Furthermore, by analogy with conventional chromatography, fundamental parameters such as retention distance, selectivity, theoretical plate number, and resolution are calculated, and optimum conditions for chromatographic separation are discussed. Based on the results obtained, the dynamic range can be extended by increasing laser power and decreasing flow rate. Peak broadening is primarily caused by variations in laser power and flow rate of the medium for large particles (< 1 microm). It is possible, in theory, to distinguish particles whose diameters differ by less than 1% for particles with a diameter larger than 1 microm. Three sizes of polystyrene beads are well separated at a flow rate of 20 microm s(-1) and a laser power of 700 mW. This technique is also applied to the separation of human erythrocytes. Two fractions, one consisting of cells ranging from 1.5 to 2.4 microm in diameter and another consisting of cells ranging from 3.5 to 5.7 microm in diameter, are observed. Optical chromatography is useful for separation and size measurement of particles and biological cells.

Supersonic Jet/Time-of-flight mass spectrometry of adenine using nanosecond and femtosecond lasers.

Mass spectra and ionization efficiencies of adenine were measured with nanosecond (15 ns) and femtosecond (500 fs) laser pulses at identical energy levels. A molecular ion is clearly observed in both spectra, but the efficiency is improved 10-fold when a femtosecond laser is used, indicating the distinct advantage of ultrashort laser pulses for multiphoton ionization of nucleobases in supersonic jet spectrometry.