Étude des mécanismes d'ablation laser par impulsions ultra-courtes à l'aide de la dynamique moléculaire

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

ZnO nanorods prepared via ablation of Zn with millisecond laser in liquid media

ZnO nanomaterials with controlled size, shape and surface chemistry are required for applications in diverse areas, such as optoelectronics, photocatalysis, biomedicine and so on. Here, we report on ZnO nanostructures with rod-like and spherical shapes prepared via laser ablation in liquid using a laser with millisecond-long pulses. By changing laser parameters (such as pulse width and peak power), the size or aspect ratio of such nanostructures could be tuned. The surface chemistry and defects of the products were also strongly affected by applied laser conditions. The preparation of different structures is explained by the intense heating of liquid media caused by millisecond-long pulses and secondary irradiation of already-formed nanostructures.

Étude des mécanismes d'ablation laser par impulsions ultra-courtes à l'aide de la dynamique moléculaire

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Elemental Analysis of Biological Matrices by Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry (LA-HR-ICP-MS) and High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

Elemental Analysis of Glass and Ink by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Laser Induced Breakdown Spectroscopy (LIBS)

The necessity of elemental analysis techniques to solve forensic problems continues to expand as the samples collected from crime scenes grow in complexity. Laser ablation ICP-MS (LA-ICP-MS) has been shown to provide a high degree of discrimination between samples that originate from different sources. In the first part of this research, two laser ablation ICP-MS systems were compared, one using a nanosecond laser and another a femtosecond laser source for the forensic analysis of glass. The results showed that femtosecond LA-ICP-MS did not provide significant improvements in terms of accuracy, precision and discrimination, however femtosecond LA-ICP-MS did provide lower detection limits. In addition, it was determined that even for femtosecond LA-ICP-MS an internal standard should be utilized to obtain accurate analytical results for glass analyses. In the second part, a method using laser induced breakdown spectroscopy (LIBS) for the forensic analysis of glass was shown to provide excellent discrimination for a glass set consisting of 41 automotive fragments. The discrimination power was compared to two of the leading elemental analysis techniques, µXRF and LA-ICP-MS, and the results were similar; all methods generated >99% discrimination and the pairs found indistinguishable were similar. An extensive data analysis approach for LIBS glass analyses was developed to minimize Type I and II errors en route to a recommendation of 10 ratios to be used for glass comparisons. Finally, a LA-ICP-MS method for the qualitative analysis and discrimination of gel ink sources was developed and tested for a set of ink samples. In the first discrimination study, qualitative analysis was used to obtain 95.6% discrimination for a blind study consisting of 45 black gel ink samples provided by the United States Secret Service. A 0.4% false exclusion (Type I) error rate and a 3.9% false inclusion (Type II) error rate was obtained for this discrimination study. In the second discrimination study, 99% discrimination power was achieved for a black gel ink pen set consisting of 24 self collected samples. The two pairs found to be indistinguishable came from the same source of origin (the same manufacturer and type of pen purchased in different locations). It was also found that gel ink from the same pen, regardless of the age, was indistinguishable as were gel ink pens (four pens) originating from the same pack.

Appendix A: LA-ICP-MS results (Laser-ablation inductively coupled plasma mass spectrometer) from monazite Moacir standard

Three samples of garnet-kyanite paragneiss from the Variscan Ulten Zone (Northern Italy) were studied in detail for U-Th-Pb monazite dating. Monazite in these gneisses is abundant, shows highly variable grain size and occupies different textural positions: within the matrix, as inclusion in garnet and kyanite, within apatite aggregates. Monazite shows different deformation features as a function of the textural position: enclosed (shielded) monazite is generally more fractured than matrix (unshielded) monazite. The integration of textural information with deformation features and in situ U-Th-Pb analyses by LA-ICP-MS indicates that there is no direct correlation between textural site and monazite ages. Old ages of 351-343 Ma, determined on portions of large matrix (unshielded) monazite and on rare domains of monazite shielded by garnet, have been related to a prograde stage of the Variscan metamorphic evolution of the Ulten Zone. Ages of 330-326 Ma, which are related to the thermal peak, are recorded by small matrix monazite, external domains of large matrix monazite, and by (domains of) fractured monazite enclosed in garnet and kyanite. Large, old unshielded grains formed as blasts during the prograde metamorphic history and survived the peak metamorphism during which crystallisation/re-crystallisation partially occurred.

Ablation of Steel by Microsecond Pulse Trains

Laser micromachining is an important material processing technique used in industry and medicine to produce parts with high precision. Control of the material removal process is imperative to obtain the desired part with minimal thermal damage to the surrounding material. Longer pulsed lasers, with pulse durations of milli- and microseconds, are used primarily for laser through-cutting and welding. In this work, a two-pulse sequence using microsecond pulse durations is demonstrated to achieve consistent material removal during percussion drilling when the delay between the pulses is properly defined. The light-matter interaction moves from a regime of surface morphology changes to melt and vapour ejection. Inline coherent imaging (ICI), a broadband, spatially-coherent imaging technique, is used to monitor the ablation process. The pulse parameter space is explored and the key regimes are determined. Material removal is observed when the pulse delay is on the order of the pulse duration. ICI is also used to directly observe the ablation process. Melt dynamics are characterized by monitoring surface changes during and after laser processing at several positions in and around the interaction region. Ablation is enhanced when the melt has time to flow back into the hole before the interaction with the second pulse begins. A phenomenological model is developed to understand the relationship between material removal and pulse delay. Based on melt refilling the interaction region, described by logistic growth, and heat loss, described by exponential decay, the model is fit to several datasets. The fit parameters reflect the pulse energies and durations used in the ablation experiments. For pulse durations of 50 us with pulse energies of 7.32 mJ +/- 0.09 mJ, the logisitic growth component of the model reaches half maximum after 8.3 us +/- 1.1 us and the exponential decays with a rate of 64 us +/- 15 us. The phenomenological model offers an interpretation of the material removal process.

Processing the Intracardiac Electrogram for Atrial Fibrillation Ablation

Atrial fibrillation (AF) is a major global health issue as it is the most prevalent sustained supraventricular arrhythmia. Catheter-based ablation of some parts of the atria is considered an effective treatment of AF. The main objective of this research is to analyze atrial intracardiac electrograms (IEGMs) and extract insightful information for the ablation therapy. Throughout this thesis we propose several computationally efficient algorithms that take streams of IEGMs from different atrial sites as the input signals, sequentially analyze them in various domains (e.g., time and frequency), and create color-coded three-dimensional map of the atria to be used in the ablation therapy.

Morphology and structure of particles produced by femtosecond laser ablation of fused silica

The aim of the present work was to study the morphology and structure of the nanoparticles produced by femtosecond laser ablation of fused silica. Ultrashort laser pulses of 1030 nm wavelength and 550 fs duration were tightly focused by a high numerical aperture microscope objective at the surface of fused silica samples while scanning the sample in relation to the stationary laser beam. Laser tracks were created with pulse energies in the range 5-100 mu J, resulting in ablation debris of different morphologies. The debris were examined by scanning and transmission electron microscopy for their morphology and crystal structure in relation to the incident laser pulse energy. Ejected particles with sizes ranging from a few nanometers to a few microns were found. Their morphologies can be broadly classified into three categories: very fine round nanoparticles with diameters lower than 20 nm, nanoparticles with intermediate sizes between 50 and 200 nm, and big irregular particles with typical size between 0.5 and 1.5 mu m. The fine nanoparticles of the first category are predominantly observed at higher pulse energies and tend to aggregate to form web-like and arborescent-like structures. The nanoparticles with intermediate sizes are observed for all pulse energies used and may appear isolated or aggregated in clusters. Finally, the larger irregular particles of the third category are observed for all energies and appear normally isolated.

Laser ablation-based one-step generation and bio-functionalization of gold nanoparticles conjugated with aptamers

Background: Bio-conjugated nanoparticles are important analytical tools with emerging biological and medical applications. In this context, in situ conjugation of nanoparticles with biomolecules via laser ablation in an aqueous media is a highly promising one-step method for the production of functional nanoparticles resulting in highly efficient conjugation. Increased yields are required, particularly considering the conjugation of cost-intensive biomolecules like RNA aptamers. Results: Using a DNA aptamer directed against streptavidin, in situ conjugation results in nanoparticles with diameters of approximately 9 nm exhibiting a high aptamer surface density (98 aptamers per nanoparticle) and a maximal conjugation efficiency of 40.3%. We have demonstrated the functionality of the aptamer-conjugated nanoparticles using three independent analytical methods, including an agglomeration-based colorimetric assay, and solid-phase assays proving high aptamer activity. To demonstrate the general applicability of the in situ conjugation of gold nanoparticles with aptamers, we have transferred the method to an RNA aptamer directed against prostate-specific membrane antigen (PSMA). Successful detection of PSMA in human prostate cancer tissue was achieved utilizing tissue microarrays. Conclusions: In comparison to the conventional generation of bio-conjugated gold nanoparticles using chemical synthesis and subsequent bio-functionalization, the laser-ablation-based in situ conjugation is a rapid, one-step production method. Due to high conjugation efficiency and productivity, in situ conjugation can be easily used for high throughput generation of gold nanoparticles conjugated with valuable biomolecules like aptamers.

Impact of radiofrequency ablation for patients with varicose veins on the budget of the German statutory health insurance system

Objectives: In contrast to other countries, surgery still represents the common invasive treatment for varicose veins in Germany. However, radiofrequency ablation, e.g. ClosureFast, becomes more and more popular in other countries due to potential better results and reduced side effects. This treatment option may cause less follow-up costs and is a more convenient procedure for patients, which could justify an introduction in the statutory benefits catalogue. Therefore, we aim at calculating the budget impact of a general reimbursement of ClosureFast in Germany. Methods: To assess the budget impact of including ClosureFast in the German statutory benefits catalogue, we developed a multi-cohort Markov model and compared the costs of a “World with ClosureFast” with a “World without ClosureFast” over a time horizon of five years. To address the uncertainty of input parameters, we conducted three different types of sensitivity analysis (one-way, scenario, probabilistic). Results: In the Base Case scenario, the introduction of the ClosureFast system for the treatment of varicose veins saves costs of about 19.1 Mio. € over a time horizon of five years in Germany. However, the results scatter in the sensitivity analyses due to limited evidence of some key input parameters. Conclusions: Results of the budget impact analysis indicate that a general reimbursement of ClosureFast has the potential to be cost-saving in the German Statutory Health Insurance.

Study of nanostructured targets for plasma production via laser ablation

Metal nanowires (NWs) - nanostructures 20-100 nm in diameter and up to tens of micrometers long - behave as waveguides when irradiated with light with wavelength much greater than their diameter. This is due to collective excitations of free electrons (plasmons) in the metal which couple to light and travel on the surface of the nanowire. This effect can be used to efficiently absorb laser pulses to produce dense and hot plasma on special nanostructured targets with metal nanowires vertically aligned on the surface. In this thesis work, nanostructured targets with different parameters (length, diameter, metal and fabrication process) have been irradiated with infrared laser light. X-ray flux emitted by the cooling plasma is measured during irradiation, and the depth of craters formed on the target is measured later. This data is used to choose which target parameters are best for plasma production. Different targets are compared with each other and against a control, non-nanostructured (bulk) target. As will be shown, highly significant (> 5 sigma) differences are found between targets with different nanostructures, and between nanostructured and bulk target. This differences are very difficult to explain whithout accounting for the nanostructures in the targets. Therefore, data collected and analized in this thesis work supports the hypotesys that nanostructured targets perform better than bulk targets for laser plasma production purposes, and provides useful indications for optimization of NWS' parameters.