Paolo Marsili

Toward the optimization of double-pulse LIBS underwater: effects of experimental parameters on the reproducibility and dynamics of laser-induced cavitation bubble

Double-pulse laser-induced breakdown spectroscopy (LIBS) was recently proposed for the analysis of underwater samples, since it overcomes the drawbacks of rapid plasma quenching and of large continuum emission, typical of single-pulse ablation. Despite the attractiveness of the method, this approach suffers nevertheless from a poor spectroscopic reproducibility, which is partially due to the scarce reproducibility of the cavitation bubble induced by the first laser pulse, since pressure and dimensions of the bubble strongly affect plasma emission. In this work, we investigated the reproducibility and the dynamics of the cavitation bubble induced on a solid target in water, and how they depend on pulse duration, energy, and wavelength, as well as on target composition. Results are discussed in terms of the effects on the laser ablation process produced by the crater formation and by the interaction of the laser pulse with floating particles and gas bubbles. This work, preliminary to the optimization of the spectroscopic signal, provides an insight of the phenomena occurring during laser ablation in water, together with useful information for the choice of the laser source to be used in the apparatus.

Dendrimer-Capped Nanoparticles Prepared by Picosecond Laser Ablation in Liquid Environment

Fifth generation ethylendiamine-core poly(amidoamine) (PAMAM G5) is presented as an efficient capping agent for the preparation of metal and semiconductor nanoparticles by ps laser ablation in water. In particular, we describe results obtained with the fundamental, second and third harmonic of a ps Nd:YAG laser and the influence of laser wavelength and pulse energy on gold particle production and subsequent photofragmentation. In this framework, the role of the dendrimer and, in particular, its interactions with gold clusters and cations are accounted.

Preparation of small size palladium nanoparticles by picosecond laser ablation and control of metal concentration in the colloid

We assessed a method for the preparation of small, highly stable and unprotected Pd nanoparticles by picosecond laser ablation in 2-propanol. The nanoparticles can be extracted from 2-propanol by centrifugation and redispersed in water, where a strongly negative ζ-potential assures long term stability. The proposed procedure permits reduction of particle size down to 1.6nm and optimization of the Pd(0):Pd(II) ratio which, in the best cases, was of the order of 6:1. The increase of this ratio with ablation times has been correlated to the high temperature conversion of PdO to metallic Pd by a simple theoretical model. A study of the relationship between colloid absorption at 400nm and Pd concentration permitted the role of PdO in the determination of the UV-vis spectra to be clarified and the limits of the Mie theory for the evaluation of colloid concentration to be established. The absorption at 400nm can be used as a fast method to estimate the Pd content in the colloids, provided that a calibration of the ablation process is preliminarily performed.

Spectroscopic measurement of ion temperature and ion velocity distributions in the flux-coil generated FRC.

One aim of the flux-coil generated field reversed configuration at Tri Alpha Energy (TAE) is to establish the plasma where the ion rotational energy is greater than the ion thermal energy. To verify this, an optical diagnostic was developed to simultaneously measure the Doppler velocity-shift and line-broadening using a 0.75 m, 1800 groves/mm, spectrometer. The output spectrum is magnified and imaged onto a 16-channel photomultiplier tube (PMT) array. The individual PMT outputs are coupled to high-gain, high-frequency, transimpedance amplifiers, providing fast-time response. The Doppler spectroscopy measurements, along with a survey spectrometer and photodiode-light detector, form a suite of diagnostics that provide insights into the time evolution of the plasma-ion distribution and current when accelerated by an azimuthal-electric field.

Antibacterial activity of silver nanoparticles obtained by pulsed laser ablation in pure water and in chloride solution

Summary Silver nanoparticles (AgNPs) have increasingly gained importance as antibacterial agents with applications in several fields due to their strong, broad-range antimicrobial properties. AgNP synthesis by pulsed laser ablation in liquid (PLAL) permits the preparation of stable Ag colloids in pure solvents without capping or stabilizing agents, producing AgNPs more suitable for biomedical applications than those prepared with common, wet chemical preparation techniques. To date, only a few investigations into the antimicrobial effect of AgNPs produced by PLAL have been performed. These have mainly been performed by ablation in water with nanosecond pulse widths. We previously observed a strong surface-enhanced Raman scattering (SERS) signal from such AgNPs by “activating” the NP surface by the addition of a small quantity of LiCl to the colloid. Such surface effects could also influence the antimicrobial activity of the NPs. Their activity, on the other hand, could also be affected by other parameters linked to the ablation conditions, such as the pulse width. The antibacterial activity of AgNPs was evaluated for NPs obtained either by nanosecond (ns) or picosecond (ps) PLAL using a 1064 nm ablation wavelength, in pure water or in LiCl aqueous solution, with Escherichia coli and Bacillus subtilis as references for Gram-negative and Gram-positive bacteria, respectively. In all cases, AgNPs with an average diameter less than 10 nm were obtained, which has been shown in previous works to be the most effective size for bactericidal activity. The measured zeta-potential values were very negative, indicating excellent long-term colloidal stability. Antibacterial activity was observed against both microorganisms for the four AgNP formulations, but the ps-ablated nanoparticles were shown to more effectively inhibit the growth of both microorganisms. Moreover, LiCl modified AgNPs were the most effective, showing minimum inhibitory concentration (MIC) values in a restricted range of 1.0–3.7 µg/mL. An explanation is proposed for this result based on the increased surface reactivity of the metal surface due to the presence of positively charged active sites.

Influence of the photon orbital angular momentum on electric dipole transitions: negative experimental evidence

We describe an experiment of atomic spectroscopy devoted to ascertaining whether the orbital angular momentum (OAM) of photons has the same property of interacting with atoms or molecules as occurs for the spin angular momentum (SAM). In our experiment, rubidium vapors are excited by means of laser radiation with different combinations of OAM and SAM, particularly selected to inhibit or enhance the fluorescence according to the selection rules for the electric dipole transitions between the fundamental state and the first excited doublet. Our results clearly show that an electric-dipole-type transition is insensitive to the OAM value, and provide an original validation of a problem long debated in theoretical works.

Doppler spectroscopy and D-alpha emission diagnostics for the C-2 FRC plasma

Two Doppler spectroscopy diagnostics with complementary capabilities are developed to measure the ion temperatures and velocities of FRC plasmas in the C-2 device. First, the multichord ion doppler diagnostic can simultaneously measure 15 chords of the plasma using an image intensified camera. Second, a single-chord fast-response ion Doppler diagnostic provides much higher faster time response by using a 16-channel photo-multiplier tube array. To study the neutral density of deuterium under different wall and plasma conditions, a highly sensitive eight-channel D-alpha diagnostic has been developed and calibrated for absolute radiance measurements. These spectroscopic diagnostics capabilities, combined with other plasma diagnostics, are helping to understand and improve the field reversed configuration plasmas in the C-2 device.

The influence of higher order waveguide modes on coherent four-wave mixing in hollow fibers

Coherent four-wave mixing (FWM) of laser pulses in gas-filled hollow fibers is studied. The experimental data and the expressions derived for the amplitude of the FWM signal indicate that the excitation of higher order waveguide modes is an important physical factor having a considerable influence on nonlinear optical processes in hollow fibers.

Metal-clad optical waveguide fluorescence device for the detection of heavy metal ions

Abstract. We developed Hg2+-sensing chips by decorating the external surface of metal-clad optical waveguides with a monolayer of Hg2+-sensitive fluorescent molecular probes. The emission properties of the original water-soluble form of the molecule were previously found to be selectively quenched in the presence of Hg2+ ions. The fabricated samples were tested with optical waveguide fluorescence spectroscopy by putting them in contact with a 5-μM water solution of Hg2+ ions and recording the emission spectra versus incubation time. The estimate of the limit of detection was 150 nM. A preliminary evaluation of the selectivity of the structure was also performed by using Cd2+ as possible interfering analytes.

Production and photofragmentation of Au nanoparticles by 355 nm picosecond radiation

Fifth generation ethylendiamine-core poly(amidoamine) (PAMAM G5)-capped-gold-nanoparticles were prepared by ps laser ablation in water, by using the third harmonic of a ps Nd:YAG laser. Post-irradiation with the same wavelength causes efficient photofragmentation of the nanoparticles. We performed a comparison with analogous tests carried out with 532 nm ps pulses. We found that, while 532-nm-fragmentation is a 2-photon photoelectric process, 355-nm-fragmentation is linear.