Photoacoustic cavitation and heat transfer effects in the laser-induced temperature jump in water

The finite element method is employed to analyze photoacoustic cavitation and heat transfer occurring when modest temperature jumps (T-jumps) are induced by a laser in D₂O solution, which may contain a small concentration of a protein or peptide sample. Cavitation can be initiated through a photoacoustic mechanism at intensities well below optical breakdown thresholds. Cavitation probability is related to test medium properties, initial temperature, T-jump magnitude and test region geometry. Parameters affecting thermal conduction losses are also examined because such losses limit the useful duration of the T-jump induced in protein folding experiments. From this study, guidelines are offered for reducing the occurrence of cavitation and extending the useful duration of the T-jump. Received: 2 April 2001 / Revised version: 17 October 2001 / Published online: 29 November 2001     

Laser ultrasound characterization of chemically prepared nano-structured silver

The ultrasonic properties of nano-structured silver (hereafter nm-Ag) are investigated by the laser ultrasonic technique. The nm-Ag superfine particles with a size of 20 to 27 nanometer (nm) are prepared by using a chemical method. Wafers of nm-Ag are fabricated under different pressing pressures and used as samples. The experimental results show that the ultrasonic velocity and attenuation of nm-Ag prepared by the chemical method depends on the pressing pressures and thus on the relative density. The elastic moduli values of nm-Ag prepared by the chemical method are deduced. The values are lower than those of polycrystalline and single-crystalline Ag. The detailed results, discussions, and comparisons with nm-Ag samples prepared by a physical method are presented. Received: 23 November 1998 / Accepted: 13 September 1999 / Published online: 24 March 2000     

Anisotropy of sound velocity for a new PbB4O7 crystal as determined by the laser ultrasonic technique

4 O₇ crystal is a new nonlinear optical crystal. For the first time the anisotropy of the velocities of its longitudinal and surface acoustic waves (SAWs) are determined by laser ultrasonic technique. The velocities of surface waves for X-, Y-, and Z-cut crystals are also calculated. The theoretical calculations of slowness curves are in good agreement with experimental results. The SAW slowness curve is elliptical for Y- or Z-cut crystal wafers, and circular for an X-cut wafer. Received: 27 January 1997/Accepted: 30 July 1997     

Absolute absorber quantification in turbid media at small source–detector separations

The aim of our studies was to develop a method to determine the absorption coefficient of a turbid medium in a reflection geometry with small source–detector separations. Therefore, the time-integrated microscopic Beer–Lambert law (MBL) was modified in order to obtain the absolute absorption coefficient from mean time of flight and dc-intensity measurements. The new technique was evaluated using turbid phantoms having varying scattering (μ_s ^′ between 0.2 and 2.2 mm^-1) and absorbing properties (μ_a between 0.04 and 0.14 mm^-1), comparable to many biological tissues at various source–detector separations between 3 and 11 mm. The measurements were performed at a wavelength of 1064 nm. We found that this new method was able to determine the absolute absorption coefficient of the selected phantoms with a standard error of less than 0.005 mm^-1 over the range of optical properties investigated. Received: 23 November 2001 / Revised version: 28 February 2002 / Published online: 14 May 2002     

Hard tissue ablation with a free running Er:YAG and a Q-switched CO2 laser: a comparative study

The Er:YAG and the CO₂ laser are competitors in the field of hard tissue ablation. The use of Er:YAG lasers (2.94 μm, pulse length _L of 100 to 200 μs) show smaller areas of thermal defects then ‘‘superpulsed’’ CO₂ lasers with pulse lengths of approximately 100 μs. Only the development of a Q-switched CO₂ laser (9.6 μm, τ_L=250 ns) allowed for similar results. In this paper new results for the Er:YAG and the Q-switched CO₂ laser under the influence of water spray will be presented. Several parameters are of special interest for these investigations: the specific ablation energy, which shows a minimum for the CO₂ laser at an energy density of 9 J/cm ² and a broad shallow minimum in the range of 10 to 70 J/cm² for the Er:YAG laser, and comparison of the cut-shape and depth. Surface effects and cutting velocity are discussed based on SEM pictures. Received: 19 July 2000 / Revised version: 1 November 2000 / Published online: 30 November 2000     

Detection of biogenic CO production above vascular cell cultures using a near-room- temperature QC-DFB laser

We report the first application of pulsed, near-room-temperature quantum cascade laser technology to the continuous detection of biogenic CO production rates above viable cultures of vascular smooth muscle cells. A computer-controlled sequence of measurements over a 9-h period was obtained, resulting in a minimum detectable CO production of 20 ppb in a 1-m optical path above a standard cell-culture flask. Data-processing procedures for real-time monitoring of both biogenic and ambient atmospheric CO concentrations are described. Received: 24 October 2001 / Published online: 29 November 2001     

Tailored ablation processing of advanced biomedical hydroxyapatite by femtosecond laser pulses

The micromachining of hydroxyapatite (HAp) is highly important for orthopedics and dentistry, since human bone and teeth consist mainly of HAp. We demonstrate ultrashort Ti:sapphire laser ablation of HAp, using pulse-widths of 50 fs, 500 fs, and 2 ps at a wavelength of 820 nm and at 1 kpps. The crucial medical issue is to preserve the chemical properties of the machined (ablated) surface. If the chemical properties of HAp change, the human bone or tooth cannot re-grow after laser processing. Using X-ray photoelectron spectroscopy, we observe chemical properties of HAp ablated in air. The HAp is ablated at laser fluences of 3.2 J/cm² (6.4×10¹³ W/cm² at 50 fs), 3.3 J/cm² (6.6×10¹² W/cm² at 500 fs), and 9.6 J/cm² (4.8×10¹² W/cm² at 2 ps), respectively. As a result it is found that the ablated surface is unchanged after laser ablation over the pulse-width range used in this experiment. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-45/566-1533, E-mail: obara@obara.elec.keio.ac.jp     

Characterization and optimization of a laser-scanning microscope in the femtosecond regime

Received: 26 August 1997/Revised version: 2 February 1998     

Reverse saturable absorption in chlorophyll A solutions

The dynamic nonlinear absorption of a chloroform solution of chlorophyll A was investigated using the Z-scan technique with picosecond pulses at 532 nm. The nonlinear absorption exhibits a reverse saturation, indicating a strong intersystem crossing (singlet–triplet) process. The time evolution of the optical nonlinearity, modeled by means of a five-level energy diagram, allows the determination of excited-state cross sections and the lifetime of the intersystem crossing based on its absorption characteristics and efficient formation of triplet states. Chlorophyll A was found to be a good candidate for a sensitizer in photodynamic therapy. Received: 14 February 2002 / Published online: 2 May 2002     

Mid-infrared laser-induced grating experiments of C2H4 and NH3 from 0.1–2 MPa and 300–800 K

Laser-induced thermal gratings (LITG) were generated in mixtures of ethylene and ammonia in nitrogen using mid-infrared laser radiation from a grating-tuned, low-pressure, pulsed (5 ms pulse width) CO₂ laser, and read out with a continuous wave Nd:YLF laser. The LITG signal intensity was measured as a function of pressure (0.1–2 MPa) and temperature (300–800 K, at 0.1 and 1 MPa) by tuning the laser to the accidental coincidences of the 10P(14) and 10R(6) emission lines with molecular absorption transitions of C₂H₄ and NH₃, respectively. Comparisons are made with theoretical predictions for the grating efficiency from a simple thermalization model. A theoretical comparison of the temporal LITG signal response for three excitation pulse shapes – a delta function, a realistic pulse, and a square wave is presented. Furthermore, it is shown that for NH₃, most of the decrease of the LITG signal intensity with increasing temperature is due to the corresponding decrease in fractional molecular absorption of the pump beam radiation. The diagnostic capabilities of the mid-infrared LITG experiment is demonstrated for spatially resolved ethylene measurements with long laser pulses in a premixed stoichiometric CH₄–air flame at atmospheric pressure. Received: 17 March 2000 / Revised version: 23 March 2000 / Published online: 13 September 2000     

Non-contact sound velocities and attenuation measurements of several ceramics at elevated temperatures

Laser ultrasonic technique has been employed to carry out the sound velocities and attenuation measurements as a function of temperature in alumina, two kinds of silicon nitride and partially stabilized zirconia (PSZ) samples. Accuracy of the laser technique used has been checked in terms of the diffraction effect and reproducibility of the results. Results of attenuation at room temperature have been compared with quartz transducer technique. In PSZ, velocity behavior has become non-linear and also, a peak in attenuation has been observed around 500 degrees C. In one of the silicon nitride sample, which uses glassy sintering agent, attenuation has shown a sharp peak around 950 degrees C. Interestingly, when the experiment was repeated from 800 to 1000 degrees C, this anomalous attenuation peak has disappeared, leaving a background increasing towards higher temperatures.     

Nonlinear side effects of fs pulses inside corneal tissue during photodisruption

In order to evaluate the potential for refractive surgery, fs laser pulses of 150-fs pulse duration were used to process corneal tissue of dead and living animal eyes. By focusing the laser radiation down to spot sizes of several microns, very precise cuts could be achieved inside the treated cornea, accompanied with minimum collateral damage to the tissue by thermal or mechanical effects. During histo-pathological analysis by light and transmission electron microscopy considerable side effects of fs photodisruption were found. Due to the high intensities at the focal region several nonlinear effects occurred. Self-focusing, photodissociation, UV-light production were observed, leading to streak formation inside the cornea. Received: 12 October 2001 / Revised version: 13 February 2002 / Published online: 14 March 2002     

Analysis of hydroxyapatite laser ablation plumes in a water atmosphere

4 m/s, shows the development of a shock wave in its front, resulting from the interaction between the species released from the target and the background gas. The water vapor slows down this component up to values of about 3×10³ m/s following a behavior that can be well described by the dynamics of a spherical shock wave. The low intensity of emission of the second component has not allowed us to analyze its dynamics. The third and slowest component expands at a constant velocity of 5×10² m/s and is constituted by hot particulates leaving the target. Spectra recorded in the shock front have shown the presence of emission lines arising from Ca I, Ca II, P I and some impurities, and two strong emission bands that can be assigned to some sort of calcium oxide. Received: 7 November 1997/Accepted: 17 February 1998     

Pulsed holmium laser ablation of tissue phantoms: correlation between bubble formation and acoustic transients

5 Pa served as tissue phantoms to evaluate such effects. Holmium laser pulses (wavelength: 2.12 μm, duration: 180 μs FWHM), were delivered through 400 and 600 μm diameter optical fibers inserted into cubes of clear gel. Bubble effects were investigated using simultaneous flash micro-videography and pressure recording for radiant exposures of 20–382 J/cm². Bubble formation and bubble collapse induced pressure transients were observed regardless of phantom stiffness. Bubbles of up to 4.2 mm in length were observed in gels with a Young’s modulus of 2.9×10⁵ Pa at a pulse energy of 650 mJ. An increase of Young’s modulus (reduction in water content) led to a monotonic reduction of bubble size. In the softest gels, bubble dimensions exceeded those observed in water. Pressure amplitudes at 3 mm decreased from 100±14 bars to 17±6 bars with increasing Young’s modulus over the studied range. Theoretical analysis suggested a major influence on bubble dynamics of the mass and energy transfer through the bubble boundary. Received: 26 August 1996/Revised version: 10 February 1997     

Dynamics of photon-induced degradation and fluorescence in riboflavin microparticles

An unexpected blue-fluorescence band (around 420 nm) from both micrometer-sized dried particles and aqueous droplets of riboflavin [7,8-dimethyl-10-(D-1^′-ribityl)-isoalloxazine] is observed when the microparticles are irradiated with a pulsed UV (355- or 351-nm) laser. The intensity of the band increases quadratically with input laser energy density (fluence) and is attributable to a one-photon-excited fluorescence of lumichrome (7,8-dimethyl-alloxazine) that is produced by photo-degradation of riboflavin. The well-known greenish-yellow fluorescence band (at 560 nm for dried particles and 535 nm for aqueous droplets) from riboflavin increases sublinearly with UV-laser fluence. With a laser input fluence above 5 J/cm² the riboflavin fluorescence decays earlier and the lumichrome fluorescence reaches a maximum later than the peak of the input laser pulse. The temporal dynamics of the 420- and 535-nm fluorescence peaks are consistent with a rate-equation simulation of photon-induced conversion of riboflavin to lumichrome and the subsequent fluorescence of lumichrome. Received: 28 September 2000 / Revised version: 11 December 2000 / Published online: 21 February 2001     

Detection of small traces of 15N2 and 14N2 by Faraday LMR spectroscopy of the corresponding isotopomers of nitric oxide

15 N₂ in a gas phase sample is described. The nitrogen is transformed by a microwave discharge into nitric oxide NO. The latter is analyzed by recording both a ¹⁵NO and a ¹⁴NO Faraday LMR signal. The determination of the transformation rate from N₂ into NO is described. The method of measurement and the achieved sensitivity (∼0.1 ppm ¹⁵N₂≈4 nanomoles ¹⁵N₂/litergas) of the spectrometer are discussed. An application in pharmacology, where ¹⁵N is used as a tracer for metabolism is indicated. First experiments with the exhalation of a rat show that the apparatus is useful to give a new quality of results. Received: 30 April 1996/Revised version: 29 July 1996     

Spectroscopic detection of biological NO with a quantum cascade laser

Two configurations of a continuous wave quantum cascade distributed feedback laser-based gas sensor for the detection of NO at a parts per billion (ppb) concentration level, typical of biomedical applications, have been investigated. The laser was operated at liquid nitrogen temperature near λ=5.2 μm. In the first configuration, a 100 m optical path length multi-pass cell was employed to enhance the NO absorption. In the second configuration, a technique based on cavity-enhanced spectroscopy (CES) was utilized, with an effective path length of 670 m. Both sensors enabled simultaneous analysis of NO and CO₂ concentrations in exhaled air. The minimum detectable NO concentration was found to be 3 ppb with a multi-pass cell and 16 ppb when using CES. The two techniques are compared, and potential future developments are discussed. Received: 1 November 2000 / Revised version: 19 January 2001 / Published online: 20 April 2001     

Evanescent-field-induced two-photon fluorescence: excitation of macroscopic areas of planar waveguides

Two-photon excitation (TPE) of fluorescence is a powerful tool for separating a faintly emitted fluorescence signal from background excitation noise. Until now TPE has only been accomplished for very small excitation areas of a few square micrometre dimensions since they are readily available in the focal zone of high-power lasers. In this paper we demonstrate, to our knowledge for the first time, two-photon excited fluorescence with planar thin-film waveguide structures of macroscopic excitation areas of the order of square millimetres to square centimetres. Based upon our results, it can be envisaged that the new combination of planar waveguide technology with TPE will become a powerful tool for macroscopic surface-interaction studies. It can also open the way for further improving the sensitivity of biosensing platforms like genomic and proteomic microarrays based upon planar waveguides. Received: 7 November 2001 / Published online: 23 November 2001     

Non-thermal ablation of neural tissue with femtosecond laser pulses

2 ; for 100 fs pulses from the same laser the experimental threshold was at 1.5 J/cm². Histopathological examinations and scanning electron micrographs confirm the high quality of the excisions. No sign of significant thermal damage was observed. Received: 29 January 1997/Revised version: 14 July 1997     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk