Ultraviolet and Deep-Ultraviolet Excitation Photothermal Heterodyne Interferometer Combined with Semi-Micro HPLC.

A detection system consisting of a photothermal heterodyne interferometer (PHI) combined with semi-micro HPLC (high-performance liquid chromatography) has been designed and investigated. An ultraviolet (UV) or deep-UV laser emitting at 375 or 213 nm, respectively, was used for the excitation of nitro-polycyclic aromatic hydrocarbons (NPAHs) and amino acids. A photothermally induced change in the refractive index of the solvent causes an optical phase difference between two arms of the interferometer, one beam passing through the photoexcited region and another used as a reference, which was sensitively detected with the PHI. The separation and detection of NPAHs and amino acids were successfully demonstrated via semi-micro HPLC with the PHI and a UV detector. The detection limits of the UV-excitation PHI for NPAHs were 1.2 - 5.2 times better than that of the commercial UV detector, although the first demonstration of deep-UV excitation suffered from significant baseline fluctuation.

Ultraviolet-Excitation Photothermal Heterodyne Interferometer as a Micro-HPLC Detector.

The first demonstration of a photothermal heterodyne interferometer (PHI) combined with micro-HPLC (high-performance liquid chromatography) is reported. A semiconductor laser (375 nm) was used for excitation, and the temperature change caused by heat released from photoexcited species was detected with a He-Ne laser (632.8 nm). The temperature-dependent refractive index change of the solvent modified the optical path of the probe beam. The phase difference between two arms of the interferometer, one passing through the heated sample and another as a reference, was sensitively detected with the PHI. The nitro-polycyclic aromatic hydrocarbon and vitamin mixture separated via micro-HPLC was successfully detected with the PHI as well as a UV detector. The detection limit of the PHI for riboflavin in the absorbance units was 77 times better than that of the commercial UV detector. The detection limit of the PHI with a small flow cell (6 nL) was the same as that with a large flow cell (18 nL) for 1-nitropyrene.

Photoionization of environmentally polluting aromatic chlorides and nitrides on the water surface by laser and synchrotron radiations.

The detection limits and photoionization thresholds of polycyclic aromatic hydrocarbons and their chlorides and nitrides on the water surface are examined using laser two-photon ionization and single-photon ionization, respectively. The laser two-photon ionization methods are highly surface-selective, with a high sensitivity for aromatic hydrocarbons tending to accumulate on the water surface in the natural environment due to their highly hydrophobic nature. The dependence of the detection limits of target aromatic molecules on their physicochemical properties (photoionization thresholds relating to excess energy, molar absorptivity, and the octanol-water partition coefficient) is discussed. The detection limit clearly depends on the product of the octanol-water partition coefficient and molar absorptivity, and no clear dependence was found on excess energy. The detection limits of laser two-photon ionization for these types of molecules on the water surface are formulated.

Estimating pH at the Air/Water Interface with a Confocal Fluorescence Microscope.

One way to determine the pH at the air/water interface with a confocal fluorescence microscope has been proposed. The relation between the pH at the air/water interface and that in a bulk solution has been formulated in connection with the adsorption equilibrium and the dissociation equilibrium of the dye adsorbed. Rhodamine B (RhB) is used as a surface-active fluorescent pH probe. The corrected fluorescence spectrum of RhB molecules at the air/water interface with the surface density of 1.0 nmol m(-2) level shows pH-dependent shifts representing an acid-base equilibrium. Two ways to determine the unknown acid-base equilibrium constant of RhB molecules at the air/water interface have been discussed. With surface-tension measurements, the adsorption properties, maximum surface density, and adsorption equilibrium constants were estimated for both cationic and zwitterionic forms of RhB molecules at the air/water interface.

Development of an anion probe: detection of sulfate ion by two-photon fluorescence of gold nanoparticles.

Anion-selective detection is demonstrated for sulfate ion in aqueous solutions by using two-photon excited fluorescence of gold nanoparticles (AuNPs) modified with a thiourea-based anion receptor, bis[2-(3-(4-nitrophenyl)thioureido)ethyl]disulfide. The fluorescent intensity increased with the change of the sulfate concentration in the solution from 10(-4) to 10(-3) M. In comparison with an unadsorbed receptor molecule in bulk acetonitrile solution, the molecule on AuNPs in water showed improved affinity for sulfate ion. The controllability of the hydrophobicity around receptor molecules on AuNPs is considered a dominant contributing factor for improved sulfate affinity. This unique feature of the surface enables us to detect anionic species in an aqueous phase where a dye-type indicator has poor sensitivity.

Mass spectrometric investigation and formation mechanisms of high-mass species in the downstream region of Ar/CF(4)/O(2) plasmas.

Mass analysis has been conducted on the positive ions and neutral species in the downstream region of Ar/CF(4)/O(2) plasmas. The neutral species have been ionized by Li(+) attachment before mass analysis. The CF(2)O(+), C(2)F(5)O(+) and C(n)F(2n-1)O(+) (1 or= 4) have been observed as the species composed only of C and F. These findings suggest that C(n)F(2n)O (n>or= 3) are produced mainly through the following reactions: CF(3)(CF(2))(m)CF = CF(2) + O((3)P) --> CF(2)((3)B(1)) + CF(3)(CF(2))(m)CFO (m>or= 1) and CF(3)(CF(2))(m)CF = CF(CF(2))(n)CF(3) + O((3)P) --> CF(3)(CF(2))(m)CF + CF(3)(CF(2))(n)CFO (m, n>or= 1), where the CF(3)(CF(2))(n)- group might have side chains, as in (CF(3))(2)CF(CF(2))(n-2)-. With the help of quantum chemistry calculations of reaction enthalpies and transition states, the formation mechanisms of the observed species have been discussed in detail.

Acidity effects on the fluorescence properties and adsorptive behavior of rhodamine 6G molecules at the air-water interface studied with confocal fluorescence microscopy.

The effects of acidity on fluorescence originated from rhodamine 6G (R6G) molecules adsorbed at the air-water interface of extremely low-concentration aqueous solutions have been studied with confocal fluorescence microscopy. Similarities and differences in the observed acidity effects between R6G molecules at the interface and those in the bulk solution have been discussed. With increasing the subphase-pH from 1 to 6, height and frequency of photon bursts as well as intensity of the interface-originated fluorescence change in two steps, while bulk fluorescence changes in one step and a little change in the number of adsorbed R6G molecules is verified with surface tension measurements. The results suggest that there is an interface-specific equilibrium among the chemical forms of R6G molecules. Chemical forms contributing to the interface-originated fluorescence above pH 5 are discussed.

Second harmonic generation from insoluble films of a rhodamine dye at the air-water interface: effect of sodium dodecylsulfate.

The second harmonic generation (SHG) from the insoluble monolayers of bis-(N-ethyl, N-octadecyl)rhodamine perchlorate (RhC18) formed on the surface of sodium dodecylsulfate (SDS) solutions of different concentrations has been studied. An enhancement of the second harmonic response was observed in the mixed films of RhC18/SDS compared to the pure-dye layer. To clarify the origin of the phenomenon, the films were characterized by surface pressure-area isotherm and reflection-absorption spectroscopy studies. The analysis of surface pressure-area isotherms of RhC18/SDS layers showed that incorporated SDS molecules essentially influence the rheological properties of the dye monolayer. The film parameters, such as the molecular surface area, maximum surface pressure, and solid-condensed phase composition, are the functions of SDS bulk concentration. A joint analysis of the SHG results and the reflection-absorption spectra revealed that the structural ordering within films was responsible for the enhancement of the nonlinear optical response, whereas the contributions from the spectral shifts and increased absorption upon aggregate formation are of less importance.

Magnification in excess of 100-times of the microscopic photothermal lensing signal from solute molecules by two-color excitation with continuous-wave lasers.

A microscopic photothermal lensing measurement under two-color continuous-wave laser excitation was performed to investigate a signal enhancement owing to the transient absorption by photoexcited solute molecules in liquid solutions. An intensity-modulated 409 nm laser beam and an un-modulated 532 nm laser beam were used for excitation, and a 670 nm probe beam was used for detecting the modulation amplitude of thermal lensing signals generated with a microscopic objective lens focusing laser beams into a capillary flow cell of 0.1 mm optical path length. The amplitude of the modulated signal increased as the power of the un-modulated laser beam increased, and a 143-times magnification was observed for an iso-propanol solution of naphthacene having 4.6 x 10(-4) absorbance at 409 nm and a negligible absorbance at 532 nm. A four-level model explaining the signal enhancement is proposed, and an important role of the transient absorption by photoexcited molecules is discussed.

Production of sound waves by bacterial cells and the response of bacterial cells to sound.

Bacterial cells enhance the proliferation of neighboring cells under stress conditions by emitting a physical signal. Continuous single sine sound waves produced by a speaker at frequencies of 6-10, 18-22, and 28-38 kHz promoted colony formation by Bacillus carboniphilus under non-permissive stress conditions of high KCl concentration and high temperature. Furthermore, sound waves emitted from cells of Bacillus subtilis at frequencies between 8 and 43 kHz with broad peaks at approximately 8.5, 19, 29, and 37 kHz were detected using a sensitive microphone system. The similarity between the frequency of the sound produced by B. subtilis and the frequencies that induced a response in B. carboniphilus and the previously observed growth-promoting effect of B. subtilis cells upon B. carboniphilus through iron barriers, suggest that the detected sound waves function as a growth-regulatory signal between cells.