Selective synthesis under microwave irradiation of new monomers for potential applications in PDLC films

Dissertation to obtain the degree of master in Bioorganic

Sawhorse-type diruthenium tetracarbonyl complexes containing porphyrin-derived ligands as highly selective photosensitizers for female reproductive cancer cells.

Diruthenium tetracarbonyl complexes of the type [Ru2(CO)4(l2-g2-O2CR)2L2] containing a Ru-Ru backbone with four equatorial carbonyl ligands, two carboxylato bridges, and two axial two-electron ligands in a sawhorse-like geometry have been synthesized with porphyrin-derived substituents in the axial ligands [1: R is CH3, L is 5-(4-pyridyl)-10,15,20-triphenyl-21,23H-porphyrin], in the bridging carboxylato ligands [2: RCO2H is 5-(4-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin, L is PPh3; 3: RCO2H is 5-(4-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin, L is 1,3,5-triaza-7-phosphatricyclo [3.3.1.1]decane], or in both positions [4: RCO2H is 5-(4-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin, L is 5-(4-pyridyl)-10,15,20-triphenyl-21,23H-porphyrin]. Compounds 1-3 were assessed on different types of human cancer cells and normal cells. Their uptake by cells was quantified by fluorescence and checked by fluorescence microscopy. These compounds were taken up by human HeLa cervix and A2780 and Ovcar ovarian carcinoma cells but not by normal cells and other cancer cell lines (A549 pulmonary, Me300 melanoma, PC3 and LnCap prostate, KB head and neck, MDAMB231 and MCF7 breast, or HT29 colon cancer cells). The compounds demonstrated no cytotoxicity in the absence of laser irradiation but exhibited good phototoxicities in HeLa and A2780 cells when exposed to laser light at 652 nm, displaying an LD50 between 1.5 and 6.5 J/cm2 in these two cell lines and more than 15 J/cm2 for the others. Thus, these types of porphyric compound present specificity for cancer cell lines of the female reproductive system and not for normal cells; thus being promising new organometallic photosensitizers.

Oral mucosal melanoma: conservative treatment including laser surgery.

Objective: To discuss the convenience of laser surgery as optimal treatment for melanoma of the oral mucosa.Patients and methods: A retrospective evaluation of four patients with primary oral melanomas treated at a single Cancer Institution in Mexico City.Results: Two patients were treated with resection of the melanoma with CO2 laser together with extraction of the involved dental organs and curettage of the alveolar walls. These two cases had melanoma in situ with multiple isolated foci. The third patient had a lesion with vertical growth, who was submitted to partial maxillectomy along with selective dissection of bilateral neck levels I-V with a negative report and the fourth patient had a history of oral nodular melanoma and presented with lymph node metastasis. According to follow-up status, there was no distant metastasis in any of the patients reported here.Conclusion: In our experience, conservative management with CO2 laser is adequate for melanomas of the oral mucosa with extraction of the dental organs and curettage of the alveoli to achieve complete surgical resection microscopically without sacrifice of the quality of life. Management of the neck is controversial. We recommend selective therapeutic resection of the neck only if it is found to be clinically positive. Elective dissection has not shown to have an impact in overall survival.

Endothelin-1-induced spreading depression in rats is associated with a microarea of selective neuronal necrosis.

Two different theories of migraine aura exist: In the vascular theory of Wolff, intracerebral vasoconstriction causes migraine aura via energy deficiency, whereas in the neuronal theory of Leão and Morison, spreading depression (SD) initiates the aura. Recently, it has been shown that the cerebrovascular constrictor endothelin-1 (ET-1) elicits SD when applied to the cortical surface, a finding that could provide a bridge between the vascular and the neuronal theories of migraine aura. Several arguments support the notion that ET-1-induced SD results from local vasoconstriction, but definite proof is missing. If ET-1 induces SD via vasoconstriction/ischemia, then neuronal damage is likely to occur, contrasting with the fact that SD in the otherwise normal cortex is not associated with any lesion. To test this hypothesis, we have performed a comprehensive histologic study of the effects of ET-1 when applied topically to the cerebral cortex of halothane-anesthetized rats. Our assessment included histologic stainings and immunohistochemistry for glial fibrillary acidic protein, heat shock protein 70, and transferase dUTP nick-end labeling assay. During ET-1 application, we recorded (i) subarachnoid direct current (DC) electroencephalogram, (ii) local cerebral blood flow by laser-Doppler flowmetry, and (iii) changes of oxyhemoglobin and deoxyhemoglobin by spectroscopy. At an ET-1 concentration of 1 muM, at which only 6 of 12 animals generated SD, a microarea with selective neuronal death was found only in those animals demonstrating SD. In another five selected animals, which had not shown SD in response to ET-1, SD was triggered at a second cranial window by KCl and propagated from there to the window exposed to ET-1. This treatment also resulted in a microarea of neuronal damage. In contrast, SD invading from outside did not induce neuronal damage in the absence of ET-1 (n = 4) or in the presence of ET-1 if ET-1 was coapplied with BQ-123, an ET(A) receptor antagonist (n = 4). In conclusion, SD in presence of ET-1 induced a microarea of selective neuronal necrosis no matter where the SD originated. This effect of ET-1 appears to be mediated by the ET(A) receptor.

Structural characterization of laser-treated Cr3C2-NiCr coatings

The interconnected porosity of the Cr3C2-NiCr coatings obtained by high-velocity oxy fuel spraying is detrimental in corrosion and wear resistance applications. Laser treatments allow sealing of their surfaces through melting and resolidification of a thin superficial layer. A Nd:YAG laser beam was used to irradiate Cr3C2-NiCr coatings either in the continuous wave mode or at different repetition rates in the pulsed one. Results indicated that high peak and low mean laser irradiances are not good, since samples presented deep grooves and an extensive crack network. At low peak and higher mean laser irradiances the surface was molten, and only a few shallow cracks were observed. The interconnected porosity was completely eliminated in a layer up to 80 m thick, formed by large Cr7C3 grains imbedded in a NiCr matrix.

Structural characterization of laser-treated Cr3C2-NiCr coatings

The interconnected porosity of the Cr3C2-NiCr coatings obtained by high-velocity oxy fuel spraying is detrimental in corrosion and wear resistance applications. Laser treatments allow sealing of their surfaces through melting and resolidification of a thin superficial layer. A Nd:YAG laser beam was used to irradiate Cr3C2-NiCr coatings either in the continuous wave mode or at different repetition rates in the pulsed one. Results indicated that high peak and low mean laser irradiances are not good, since samples presented deep grooves and an extensive crack network. At low peak and higher mean laser irradiances the surface was molten, and only a few shallow cracks were observed. The interconnected porosity was completely eliminated in a layer up to 80 m thick, formed by large Cr7C3 grains imbedded in a NiCr matrix.

Nd:YAG Laser Welding of 5083 Aluminium Alloy using Filler Wire

High reflectivity and high thermal conductivity, high vapour pressure of alloyingelements as well as low liquid surface tension and low ionisation potential, make laser welding of aluminium and its alloys a demanding task.Problems that occur during welding are mainly process instabilities of the keyhole and the melt pool, increased plasma formation above the melt pool and loss of alloying elements. These problems lead to unwanted metallurgical defects like hot cracks and porosity in the weld bead andother problems concerning the shape and appearance of the weld bead. In order to minimise the defects and improve the weld quality, the process and beam parameters need to be carefully adjusted along with a consideration concerning the use of filler wire for the welding process. In this work the welding of 3,0 mm thick grade 5083 aluminium alloy plates using a 3,0 kW Nd:YAG laser with grade 5183 filler wire addition is investigated. The plates were welded as butt joints with air gap sizes 0,5 mm, 0,7mm and 1,0 mm. The analysis of the weld beads obtained from the weldedsamples showed that the least imperfections were produced with 0,7 mm air gaps at moderate welding speeds. The analysis also covered the calculation of the melting efficiency and the study of the shape of the weld bead. The melting efficiency was on average around 20 % for the melting process of the welded plates. The weld beads showed the characteristic V-shape of a laser weld and retained this shape during the whole series of experiments.

Performance of high power fibre laser cutting of thick-section steel and mediumsection aluminium

Cutting of thick section stainless steel and mild steel, and medium section aluminium using the high power ytterbium fibre laser has been experimentally investigated in this study. Theoretical models of the laser power requirement for cutting of a metal workpiece and the melt removal rate were also developed. The calculated laser power requirement was correlated to the laser power used for the cutting of 10 mm stainless steel workpiece and 15 mm mild steel workpiece using the ytterbium fibre laser and the CO2 laser. Nitrogen assist gas was used for cutting of stainless steel and oxygen was used for mild steel cutting. It was found that the incident laser power required for cutting at a given cutting speed was lower for fibre laser cutting than for CO2 laser cutting indicating a higher absorptivity of the fibre laser beam by the workpiece and higher melting efficiency for the fibre laser beam than for the CO2 laser beam. The difficulty in achieving an efficient melt removal during high speed cutting of the 15 mmmild steel workpiece with oxygen assist gas using the ytterbium fibre laser can be attributed to the high melting efficiency of the ytterbium fibre laser. The calculated melt flow velocity and melt film thickness correlated well with the location of the boundary layer separation point on the 10 mm stainless steel cut edges. An increase in the melt film thickness caused by deceleration of the melt particles in the boundary layer by the viscous shear forces results in the flow separation. The melt flow velocity increases with an increase in assist gas pressure and cut kerf width resulting in a reduction in the melt film thickness and the boundary layer separation point moves closer to the bottom cut edge. The cut edge quality was examined by visual inspection of the cut samples and measurement of the cut kerf width, boundary layer separation point, cut edge squareness (perpendicularity) deviation, and cut edge surface roughness as output quality factors. Different regions of cut edge quality in 10 mm stainless steel and 4 mm aluminium workpieces were defined for different combinations of cutting speed and laserpower.Optimization of processing parameters for a high cut edge quality in 10 mmstainless steel was demonstrated

Characterization Of Process Efficiency Improvement In Laser Additive Manufacturing

Laser additive manufacturing (LAM), known also as 3D printing, has gained a lot of interest in past recent years within various industries, such as medical and aerospace industries. LAM enables fabrication of complex 3D geometries by melting metal powder layer by layer with laser beam. Research in laser additive manufacturing has been focused in development of new materials and new applications in past 10 years. Since this technology is on cutting edge, efficiency of manufacturing process is in center role of research of this industry. Aim of this thesis is to characterize methods for process efficiency improvements in laser additive manufacturing. The aim is also to clarify the effect of process parameters to the stability of the process and in microstructure of manufactured pieces. Experimental tests of this thesis were made with various process parameters and their effect on build pieces has been studied, when additive manufacturing was performed with a modified research machine representing EOSINT M-series and with EOS EOSINT M280. Material used was stainless steel 17-4 PH. Also, some of the methods for process efficiency improvements were tested. Literature review of this thesis presents basics of laser additive manufacturing, methods for improve the process efficiency and laser beam – material- interaction. It was observed that there are only few public studies about process efficiency of laser additive manufacturing of stainless steel. According to literature, it is possible to improve process efficiency with higher power lasers and thicker layer thicknesses. The process efficiency improvement is possible if the effect of process parameter changes in manufactured pieces is known. According to experiments carried out in this thesis, it was concluded that process parameters have major role in single track formation in laser additive manufacturing. Rough estimation equations were created to describe the effect of input parameters to output parameters. The experimental results showed that the WDA (width-depth-area of cross-sections of single track) is correlating exponentially with energy density input. The energy density input is combination of the input parameters of laser power, laser beam spot diameter and scan speed. The use of skin-core technique enables improvement of process efficiency as the core of the part is manufactured with higher laser power and thicker layer thickness and the skin with lower laser power and thinner layer thickness in order to maintain high resolution. In this technique the interface between skin and core must have overlapping in order to achieve full dense parts. It was also noticed in this thesis that keyhole can be formed in LAM process. It was noticed that the threshold intensity value of 106 W/cm2 was exceeded during the tests. This means that in these tests the keyhole formation was possible.

Étude par dynamique moléculaire de l'ablation par impulsions laser ultrabrèves de cibles nanocristallines

L’ablation de cibles d’Al nanocristallines (taille moyenne des cristallites d = 3,1 et 6,2 nm) par impulsions laser ultrabrèves (200 fs) a été étudiée par l’entremise de si- mulations combinant la dynamique moléculaire et le modèle à deux températures (two- temperature model, TTM) pour des fluences absorbées allant de 100 à 1300 J/m2. Nos simulations emploient un potentiel d’interaction de type EAM et les propriétés électro- niques des cibles en lien avec le TTM sont représentées par un modèle réaliste possédant une forme distincte dans le solide monocristallin, le solide nanocristallin et le liquide. Nous avons considéré l’effet de la taille moyenne des cristallites de même que celui de la porosité et nous avons procédé à une comparaison directe avec des cibles mono- cristallines. Nous avons pu montrer que le seuil d’ablation des métaux nanocristallins est significativement plus bas, se situant à 400 J/m2 plutôt qu’à 600 J/m2 dans le cas des cibles monocristallines, l’écart étant principalement dû à l’onde mécanique plus im- portante présente lors de l’ablation. Leur seuil de spallation de la face arrière est aussi significativement plus bas de par la résistance à la tension plus faible (5,40 GPa contre 7,24 GPa) des cibles nanocristallines. Il est aussi apparu que les contraintes résiduelles accompagnant généralement l’ablation laser sont absentes lors de l’ablation de cibles d’aluminium nanocristallines puisque la croissance cristalline leur permet d’abaisser leur volume spécifique. Nos résultats indiquent aussi que le seuil de fusion des cibles nano- cristallines est réduit de façon marquée dans ces cibles ce qui s’explique par la plus faible énergie de cohésion inhérente à ces matériaux. Nos simulations permettent de montrer que les propriétés structurelles et électroniques propres aux métaux nanocristallins ont toutes deux un impact important sur l’ablation.

Ablation laser femtoseconde de verres métalliques de Cu_x Zr_(1−x) : une étude par dynamique moléculaire

L’ablation laser de verres métalliques de CuxZr1−x (x = 0.33, 0.50 et 0.67) et d’un alliage métallique cristallin de CuZr2 dans la structure C11b a été étudiée par dynamique moléculaire (DM) combinée à un modèle à deux températures (TTM). Le seuil d’ablation (Fth) a été déterminé pour chacun des 4 échantillons et s'est avéré plus bas pour les échantillons plus riches en Cu étant donné que la cohésion du Cu est plus faible que celle du Zr dans tous les échantillons. Pour x=0.33, Fth est plus bas pour le cristal que pour l’amorphe car le couplage électron-phonon est plus faible dans ce dernier, ce qui implique que l’énergie est transférée plus lentement du système électronique vers le système ionique pour le a-CuZr2 que le c-CuZr2. La vitesse de l’onde de pression créée par l’impact du laser croît avec la fluence dans l’échantillon cristallin, contrairement aux échantillons amorphes dans lesquels sa vitesse moyenne est relativement constante avec la fluence. Ceci est expliqué par le fait que le module de cisaillement croît avec la pression pour le cristal, ce qui n’est pas le cas pour les verres métalliques étudiés. Finalement, la zone affectée par la chaleur (HAZ) a été étudiée via la profondeur de fusion et les déformations plastiques. La plus faible température de fusion des échantillons amorphes implique que la profondeur de fusion est plus importante dans ceux-ci que dans l’échantillon cristallin. Dans les verres métalliques, les déformations plastiques ont été identifiées sous forme de zones de transformation par cisaillement (STZ) qui diffusent et fusionnent à plus haute fluence. Aucune déformation plastique importante n’a été identifiée dans le c-CuZr2 mis à part de légères déformations près du front de fusion causées par les contraintes résiduelles. Ce travail a ainsi permis d’améliorer notre compréhension de l’ablation laser sur les verres métalliques et de l’étendue des dommages qu’elle peut entraîner.

Evaluation of laser ablation threshold in polymer samples using pulsed photoacoustic technique

The acoustic signals generated in solids due to interaction with pulsed laser beam is used to determine the ablation threshold of bulk polymer samples of teflon (polytetrafluoroethylene) and nylon under the irradiation from a Q-switched Nd:YAG laser at 1.06µm wavelength. A suitably designed piezoelectric transducer is employed for the detection of photoacoustic (PA) signals generated in this process. It has been observed that an abrupt increase in the amplitude of the PA signal occurs at the ablation threshold. Also there exist distinct values for the threshold corresponding to different mechanisms operative in producing damages like surface morphology, bond breaking and melting processes at different laser energy densities.

Selective mode excitation in dye-doped DNA polyvinyl alcohol thin film

A solid-state laser based on a dye-doped deoxyribonucleic acid (DNA) matrix is described. A thin solid film of DNA has been fabricated by treating with polyvinyl alcohol (PVA) and used as a host for the laser dye Rhodamine 6G. The edge emitted spectrum clearly indicated the existence of laser modes and amplified spontaneous emission. Lasing was obtained by pumping with a frequency-doubled Nd:YAG laser at 532 nm. For a pump energy of 10 mJ/pulse, an intense line with FWHM ≈0.2 nm was observed at 566 nm due to selective mode excitation.

Theory of laser-induced ultrafast structural changes in solids

The present thesis is a contribution to the study of laser-solid interaction. Despite the numerous applications resulting from the recent use of laser technology, there is still a lack of satisfactory answers to theoretical questions regarding the mechanism leading to the structural changes induced by femtosecond lasers in materials. We provide here theoretical approaches for the description of the structural response of different solids (cerium, samarium sulfide, bismuth and germanium) to femtosecond laser excitation. Particular interest is given to the description of the effects of the laser pulse on the electronic systems and changes of the potential energy surface for the ions. Although the general approach of laser-excited solids remains the same, the potential energy surface which drives the structural changes is calculated with different theoretical models for each material. This is due to the difference of the electronic properties of the studied systems. We use the Falicov model combined with an hydrodynamic method to study photoinduced phase changes in cerium. The local density approximation (LDA) together with the Hubbard-type Hamiltonian (LDA+U) in the framework of density functional theory (DFT) is used to describe the structural properties of samarium sulfide. We parametrize the time-dependent potential energy surface (calculated using DFT+ LDA) of bismuth on which we perform quantum dynamical simulations to study the experimentally observed amplitude collapse and revival of coherent $A_{1g}$ phonons. On the basis of a time-dependent potential energy surface calculated from a non-orthogonal tight binding Hamiltonian, we perform molecular dynamics simulation to analyze the time evolution (coherent phonons, ultrafast nonthermal melting) of germanium under laser excitation. The thermodynamic equilibrium properties of germanium are also reported. With the obtained results we are able to give many clarifications and interpretations of experimental results and also make predictions.

Highly Sensitive Sensor Based On Intracavity Laser Absorption Spectroscopy By Means of Relative Intensity Noise

This thesis concerns with the main aspects of medical trace molecules detection by means of intracavity laser absorption spectroscopy (ICLAS), namely with the equirements for highly sensitive, highly selective, low price, and compact size sensor. A novel two modes semiconductor laser sensor is demonstrated. Its operation principle is based on the competition between these two modes. The sensor sensitivity is improved when the sample is placed inside the two modes laser cavity, and the competition between the two modes exists. The effects of the mode competition in ICLAS are discussed theoretically and experimentally. The sensor selectivity is enhanced using external cavity diode laser (ECDL) configuration, where the tuning range only depends on the external cavity configuration. In order to considerably reduce the sensor cost, relative intensity noise (RIN) is chosen for monitoring the intensity ratio of the two modes. RIN is found to be an excellent indicator for the two modes intensity ratio variations which strongly supports the sensor methodology. On the other hand, it has been found that, wavelength tuning has no effect on the RIN spectrum which is very beneficial for the proposed detection principle. In order to use the sensor for medical applications, the absorption line of an anesthetic sample, propofol, is measured. Propofol has been dissolved in various solvents. RIN has been chosen to monitor the sensor response. From the measured spectra, the sensor sensitivity enhancement factor is found to be of the order of 10^(3) times of the conventional laser spectroscopy.