“Investigations on Vibrational Overtones in the NIR region and Laser Induced Fluorescence in some selected compounds”

The central theme of this research concerns the study of vibrationally excited molecules. We have used the local mode description of such vibrational states, and this -model has now gained general acceptance. A central feature of the model is the Wloealizafion of vibrational energy. A study of these high—energy localized states provides example, becauseof this localization, overtone spectra, which measure the absorption of T vibrational energy, are extremely sensitive to the properties of X-H bonds. We also use -overtone spectra to study the conformation of molecules, i.e., the relative internal orientation of their bonds. The thesis comprises six chapters

Swift heavy ion induced surface modification for tailoring coercivity in Fe–Ni based amorphous thin films

Fe–Ni based amorphous thin films were prepared by thermal evaporation. These films were irradiated by 108 MeV Ag8+ ions at room temperature with fluences ranging from 1 1012 to 3 1013 ions/cm2 using a 15 UD Pelletron accelerator. Glancing angle x-ray diffraction studies showed that the irradiated films retain their amorphous nature. The topographical evolution of the films under swift heavy ion SHI bombardment was probed using atomic force microscope and it was noticed that surface roughening was taking place with ion beam irradiation. Magnetic measurements using a vibrating sample magnetometer showed that the coercivity of the films increases with an increase in the ion fluence. The observed coercivity changes are correlated with topographical evolution of the films under SHI irradiation. The ability to modify the magnetic properties via SHI irradiation could be utilized for applications in thin film magnetism

Swift heavy ion induced surface and microstructural evolution in metallic glass thin films

Swift heavy ion induced changes in microstructure and surface morphology of vapor deposited Fe–Ni based metallic glass thin films have been investigated by using atomic force microscopy, X-ray diffraction and transmission electron microscopy. Ion beam irradiation was carried out at room temperature with 103 MeV Au9+ beam with fluences ranging from 3 1011 to 3 1013 ions/cm2. The atomic force microscopy images were subjected to power spectral density analysis and roughness analysis using an image analysis software. Clusters were found in the image of as-deposited samples, which indicates that the film growth is dominated by the island growth mode. As-deposited films were amorphous as evidenced from X-ray diffraction; however, high resolution transmission electron microscopy measurements revealed a short range atomic order in the samples with crystallites of size around 3 nm embedded in an amorphous matrix. X-ray diffraction pattern of the as-deposited films after irradiation does not show any appreciable changes, indicating that the passage of swift heavy ions stabilizes the short range atomic ordering, or even creates further amorphization. The crystallinity of the as-deposited Fe–Ni based films was improved by thermal annealing, and diffraction results indicated that ion beam irradiation on annealed samples results in grain fragmentation. On bombarding annealed films, the surface roughness of the films decreased initially, then, at higher fluences it increased. The observed change in surface morphology of the irradiated films is attributed to the interplay between ion induced sputtering, volume diffusion and surface diffusion

Contact potential induced enhancement of magnetization in polyaniline coated nanomagnetic iron oxides by plasma polymerization

The present work derives motivation from the so called surface/interfacial magnetism in core shell structures and commercial samples of Fe3O4 and c Fe2O3 with sizes ranging from 20 to 30 nm were coated with polyaniline using plasma polymerization and studied. The High Resolution Transmission Electron Microscopy images indicate a core shell structure after polyaniline coating and exhibited an increase in saturation magnetization by 2 emu/g. For confirmation, plasma polymerization was performed on maghemite nanoparticles which also exhibited an increase in saturation magnetization. This enhanced magnetization is rather surprising and the reason is found to be an interfacial phenomenon resulting from a contact potential.

Magnetic and topographical modifications of amorphous Co–Fe thin films induced by high energy Ag7+ ion irradiation

We have investigated the effects of swift heavy ion irradiation on thermally evaporated 44 nm thick, amorphous Co77Fe23 thin films on silicon substrates using 100 MeV Ag7+ ions fluences of 1 1011 ions/ cm2, 1 1012 ions/cm2, 1 1013 ions/cm2, and 3 1013 ions/cm2. The structural modifications upon swift heavy irradiation were investigated using glancing angle X-ray diffraction. The surface morphological evolution of thin film with irradiation was studied using Atomic Force Microscopy. Power spectral density analysis was used to correlate the roughness variation with structural modifications investigated using X-ray diffraction. Magnetic measurements were carried out using vibrating sample magnetometry and the observed variation in coercivity of the irradiated films is explained on the basis of stress relaxation. Magnetic force microscopy images are subjected to analysis using the scanning probe image processor software. These results are in agreement with the results obtained using vibrating sample magnetometry. The magnetic and structural properties are correlated

Mn2þ-induced room-temperature ferromagnetism and spin-glass behavior in hydrothermally grown Mn-doped ZnO nanorods

The magnetic properties of Mn-doped ZnO (ZnO:Mn) nanorods grown by hydrothermal process at a temperature of 200 8C and a growth time of 3 h have been studied. The samples were characterized by using powder X-ray diffraction with Rietveld refinement, scanning electron microscopy, energy-dispersive X-ray analysis and SQUID magnetometry. Mn (3 wt%) and (5 wt%)-doped ZnO samples exhibit paramagnetic and ferromagnetic behavior, respectively, at room temperature. The spin-glass behavior is observed from the samples with respect to the decrease of temperature. At 10 K, both samples exhibit a hysteresis loop with relatively low coercivity. The room-temperature ferromagnetism in 5 wt% Mn-doped ZnO nanorods is attributed to the increase in the specific area of grain boundaries, interaction between dopant Mn2þ ions substituted at Zn2þ site and the interaction between Mn2þ ions and Zn2þ ions from the ZnO host lattice

Absolute Kr 4s-electron photoionization cross sections between 30 and 90 eV measured by photon-induced fluorescence spectroscopy (PIFS)

Absolute Kr 4s-electron photoionization cross sections as a function of the exciting-photon energy between 30 and 90 eV were measured by photon-induced fluorescence spectroscopy (PIFS). The measurements were compared with available experimental data and theoretical calculations.

Atomistic-continuum modeling of ultrafast laser-induced melting of silicon targets

In this work, we present an atomistic-continuum model for simulations of ultrafast laser-induced melting processes in semiconductors on the example of silicon. The kinetics of transient non-equilibrium phase transition mechanisms is addressed with MD method on the atomic level, whereas the laser light absorption, strong generated electron-phonon nonequilibrium, fast heat conduction, and photo-excited free carrier diffusion are accounted for with a continuum TTM-like model (called nTTM). First, we independently consider the applications of nTTM and MD for the description of silicon, and then construct the combined MD-nTTM model. Its development and thorough testing is followed by a comprehensive computational study of fast nonequilibrium processes induced in silicon by an ultrashort laser irradiation. The new model allowed to investigate the effect of laser-induced pressure and temperature of the lattice on the melting kinetics. Two competing melting mechanisms, heterogeneous and homogeneous, were identified in our big-scale simulations. Apart from the classical heterogeneous melting mechanism, the nucleation of the liquid phase homogeneously inside the material significantly contributes to the melting process. The simulations showed, that due to the open diamond structure of the crystal, the laser-generated internal compressive stresses reduce the crystal stability against the homogeneous melting. Consequently, the latter can take a massive character within several picoseconds upon the laser heating. Due to the large negative volume of melting of silicon, the material contracts upon the phase transition, relaxes the compressive stresses, and the subsequent melting proceeds heterogeneously until the excess of thermal energy is consumed. A series of simulations for a range of absorbed fluences allowed us to find the threshold fluence value at which homogeneous liquid nucleation starts contributing to the classical heterogeneous propagation of the solid-liquid interface. A series of simulations for a range of the material thicknesses showed that the sample width we chosen in our simulations (800 nm) corresponds to a thick sample. Additionally, in order to support the main conclusions, the results were verified for a different interatomic potential. Possible improvements of the model to account for nonthermal effects are discussed and certain restrictions on the suitable interatomic potentials are found. As a first step towards the inclusion of these effects into MD-nTTM, we performed nanometer-scale MD simulations with a new interatomic potential, designed to reproduce ab initio calculations at the laser-induced electronic temperature of 18946 K. The simulations demonstrated that, similarly to thermal melting, nonthermal phase transition occurs through nucleation. A series of simulations showed that higher (lower) initial pressure reinforces (hinders) the creation and the growth of nonthermal liquid nuclei. For the example of Si, the laser melting kinetics of semiconductors was found to be noticeably different from that of metals with a face-centered cubic crystal structure. The results of this study, therefore, have important implications for interpretation of experimental data on the kinetics of melting process of semiconductors.

An update of the mechanisms of resistance to EGFR-tyrosine kinase inhibitors in breast cancer: gefitinib (Iressatrade mark)-induced changes in the expression and nucleo-cytoplasmic trafficking of HER-ligands (Review)

Intrinsic resistance to the epidermal growth factor receptor (EGFR; HER1) tyrosine kinase inhibitor (TKI) gefitinib, and more generally to EGFR TKIs, is a common phenomenon in breast cancer. The availability of molecular criteria for predicting sensitivity to EGFR-TKIs is, therefore, the most relevant issue for their correct use and for planning future research. Though it appears that in non-small-cell lung cancer (NSCLC) response to gefitinib is directly related to the occurrence of specific mutations in the EGFR TK domain, breast cancer patients cannot be selected for treatment with gefitinib on the same basis as such EGFR mutations have been reported neither in primary breast carcinomas nor in several breast cancer cell lines. Alternatively, there is a general agreement on the hypothesis that the occurrence of molecular alterations that activate transduction pathways downstream of EGFR (i.e., MEK1/MEK2 - ERK1/2 MAPK and PI-3'K - AKT growth/survival signaling cascades) significantly affect the response to EGFR TKIs in breast carcinomas. However, there are no studies so far addressing a role of EGF-related ligands as intrinsic breast cancer cell modulators of EGFR TKI efficacy. We recently monitored gene expression profiles and sub-cellular localization of HER-1/-2/-3/-4 related ligands (i.e., EGF, amphiregulin, transforming growth factor-α, ß-cellulin, epiregulin and neuregulins) prior to and after gefitinib treatment in a panel of human breast cancer cell lines. First, gefitinibinduced changes in the endogenous levels of EGF-related ligands correlated with the natural degree of breast cancer cell sensitivity to gefitinib. While breast cancer cells intrinsically resistant to gefitinib (IC50 ≥15 μM) markedly up-regulated (up to 600 times) the expression of genes codifying for HERspecific ligands, a significant down-regulation (up to 106 times) of HER ligand gene transcription was found in breast cancer cells intrinsically sensitive to gefitinib (IC50 ≤1 μM). Second, loss of HER1 function differentially regulated the nuclear trafficking of HER-related ligands. While gefitinib treatment induced an active import and nuclear accumulation of the HER ligand NRG in intrinsically gefitinib-resistant breast cancer cells, an active export and nuclear loss of NRG was observed in intrinsically gefitinib-sensitive breast cancer cells. In summary, through in vitro and pharmacodynamic studies we have learned that, besides mutations in the HER1 gene, oncogenic changes downstream of HER1 are the key players regulating gefitinib efficacy in breast cancer cells. It now appears that pharmacological inhibition of HER1 function also leads to striking changes in both the gene expression and the nucleo-cytoplasmic trafficking of HER-specific ligands, and that this response correlates with the intrinsic degree of breast cancer sensitivity to the EGFR TKI gefitinib. The relevance of this previously unrecognized intracrine feedback to gefitinib warrants further studies as cancer cells could bypass the antiproliferative effects of HER1-targeted therapeutics without a need for the overexpression and/or activation of other HER family members and/or the activation of HER-driven downstream signaling cascades

Toxina botulínica en manejo de síntomas del tracto urinario bajo en pacientes con hiperplasia prostática benigna - revisión sistemática de la literatura

Revisión sistemática de la literatura tomando ensayos clínicos aleatorizados sobre el uso de la inyección intraprostática de la toxina botulínica en los pacientes con hiperplasia prostática benigna evaluando una escala validada de síntomas del tracto urinario bajo como desenlace primario

Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

A case study of the radiative forcing of persistent contrails evolving into contrail-induced cirrus

The radiative forcing due to a distinct pattern of persistent contrails that form into contrail-induced cirrus near and over the UK is investigated in detail for a single case study during March 2009. The development of the contrail-induced cirrus is tracked using a number of high-resolution polar orbiting and lower-resolution geostationary satellite instruments and is found to persist for a period of around 18 h, and at its peak, it covers over 50,000 km2. The shortwave (SW) and longwave (LW) radiative forcing of the contrail-induced cirrus is estimated using a combination of geostationary satellite instruments, numerical weather prediction models, and surface observation sites. As expected, the net radiative effect is a relatively small residual of the much stronger but opposing SW and LW effects, locally totaling around 10 W m−2 during daylight hours and 30 W m−2 during nighttime. A simple estimate indicates that this single localized event may have generated a global-mean radiative forcing of around 7% of recent estimates of the persistent contrail radiative forcing due to the entire global aircraft fleet on a diurnally averaged basis. A single aircraft operating in conditions favorable for persistent contrail formation appears to exert a contrail-induced radiative forcing some 5000 times greater (in W m−2 km−1) than recent estimates of the average persistent contrail radiative forcing from the entire civil aviation fleet. This study emphasizes the need to establish whether similar events are common or highly unusual for a confident assessment of the total climate effect of aviation to be made.