Generation of Naphthoquinone Radical Anions by Electrospray Ionization: Solution, Gas-Phase, and Computational Chemistry Studies

Radical anions are present in several chemical processes, and understanding the reactivity of these species may be described by their thermodynamic properties. Over the last years, the formation of radical ions in the gas phase has been an important issue concerning electrospray ionization mass spectrometry studies. In this work, we report on the generation of radical anions of quinonoid compounds (Q) by electrospray ionization mass spectrometry. The balance between radical anion formation and the deprotonated molecule is also analyzed by influence of the experimental parameters (gas-phase acidity, electron affinity, and reduction potential) and solvent system employed. The gas-phase parameters for formation of radical species and deprotonated species were achieved on the basis of computational thermochemistry. The solution effects on the formation of radical anion (Q(center dot-)) and dianion (Q(2-)) were evaluated on the basis of cyclic voltammetry analysis and the reduction potentials compared with calculated electron affinities. The occurrence of unexpected ions [Q + 15](-) was described as being a reaction between the solvent system and the radical anion, Q(center dot-).The gas-phase chemistry of the electrosprayed radical anions was obtained by collisional-induced dissociation and compared to the relative energy calculations. These results are important for understanding the formation and reactivity of radical anions and to establish their correlation with the reducing properties by electrospray ionization analyses.

Electron energy loss spectroscopy: physical principles, state of the art and applications to the nanosciences

In the present work we review the way in which the electron-matter interaction allows us to perform electron energy loss spectroscopy (EELS), as well as the latest developments in the technique and some of the most relevant results of EELS as a characterization tool in nanoscience and nanotechnology.

Investigation of resins suitable for the preparation of biological sample for 3-D electron microscopy.

In the last two decades, the third-dimension has become a focus of attention in electron microscopy to better understand the interactions within subcellular compartments. Initially, transmission electron tomography (TEM tomography) was introduced to image the cell volume in semi-thin sections (∼500nm). With the introduction of the focused ion beam scanning electron microscope, a new tool, FIB-SEM tomography, became available to image much larger volumes. During TEM tomography and FIB-SEM tomography, the resin section is exposed to a high electron/ion dose such that the stability of the resin embedded biological sample becomes an important issue. The shrinkage of a resin section in each dimension, especially in depth, is a well-known phenomenon. To ensure the dimensional integrity of the final volume of the cell, it is important to assess the properties of the different resins and determine the formulation which has the best stability in the electron/ion beam. Here, eight different resin formulations were examined. The effects of radiation damage were evaluated after different times of TEM irradiation. To get additional information on mass-loss and the physical properties of the resins (stiffness and adhesion), the topography of the irradiated areas was analysed with atomic force microscopy (AFM). Further, the behaviour of the resins was analysed after ion milling of the surface of the sample with different ion currents. In conclusion, two resin formulations, Hard Plus and the mixture of Durcupan/Epon, emerged that were considerably less affected and reasonably stable in the electron/ion beam and thus suitable for the 3-D investigation of biological samples.

On the formulation and the calculation of the harmonic contributions to the Debye-Waller factor in metals (sodium)

The algebraic expressions for the anharmonic contributions to the Debye-Waller factor up to 0(A ) and 0 L% ) £ where ^ is the scattering wave-vector] have been derived in a form suitable for cubic metals with small ion cores where the interatomic potential extends to many neighbours. This has been achieved in terms of various wave-vector dependent tensors, following the work of Shukla and Taylor (1974) on the cubic anharmonic Helmholtz free energy. The contribution to the various wave-vector dependent tensors from the coulomb and the electron-ion terms in the interatomic metallic potential has been obtained by the Ewald procedure. All the restricted multiple whole B r i l l o u i n zone (B.Z.) sums are reduced to single whole B.Z. sums by using the plane wave representation of the delta function. These single whole B.Z. sums are further reduced to the •%?? portion of the B.Z. following Shukla and Wilk (1974) and Shukla and Taylor (1974). Numerical calculations have been performed for sodium where the Born-Mayer term in the interatomic potential has been neglected because i t is small £ Vosko (1964)3 • *n o^er to compare our calculated results with the experimental results of Dawton (1937), we have also calculated the r a t io of the intensities at different temperatures for the lowest five reflections (110), (200), (220), (310) and (400) . Our calculated quasi-harmonic results agree reasonably well with the experimental results at temperatures (T) of the order of the Debye temperature ( 0 ). For T » © ^ 9 our calculated anharmonic results are found to be in good agreement with the experimental results.The anomalous terms in the Debye-Waller factor are found not to be negligible for certain reflections even for T ^ ©^ . At temperature T yy Op 9 where the temperature is of the order of the melting temperature (Xm) » "the anomalous terms are found to be important almost for all the f i ve reflections.

Structural and spectroscopic properties of the diazocarbene radical (CNN) and its ions CNN(+) and CNN(-): a high-level theoretical investigation

The diazocarbene radical, CNN, and the ions CNN(+) and CNN(-) were investigated at a high level of theory. Very accurate structural parameters for the states X(3)Sigma(-) and A(3)Pi of CNN, and X(2)Pi of both CNN(+) and CNN(-) were obtained with the UCCSD(T) method using correlated-consistent basis functions with extrapolations to the complete basis set limit, with valence only and also with all electrons correlated. Harmonic and anharmonic frequencies were obtained for all species and the Renner parameter and average frequencies evaluated for the Pi states. At the UCCSD(T)/CBS(T-5) level of theory, Delta(f)H(0 K) = 138.89 kcal/mol and Delta(f)H(298 K) = 139.65 kcal/mol were obtained for diazocarbene; for the ionization potential and the electron affinity of CNN, 10.969 eV (252.95 kcal/mol), and 1.743 eV (40.19 kcal/mol), respectively, are predicted. Geometry optimization was also carried out with the CASSCF/MRCI/CBS(T-5) approach for the states X(3)Sigma(-) A(3)Pi, and a(1)Delta of CNN, and with the CASSCF/MRSDCI/aug-cc-pVTZ approach for the states b(1)Sigma(+), c(1)Pi, d(1)Sigma(-), and B(3)Sigma(-), and excitation energies (T(e)) evaluated. Vertical energies were calculated for 15 electronic states, thus improving on the accuracy of the five transitions already described, and allowing for a reliable overview of a manifold of other states, which is expected to guide future spectroscopic experiments. This study corroborates the experimental assignment for the vertical transition X (3)Sigma(-) <- E (3)Pi.

Rare earth centers properties and electron trapping in SnO2 thin films produced by sol-gel route

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Interaction of human neutrophils with endothelial cells regulates the expression of endogenous proteins annexin 1, galectin-1 and galectin-3

Annexin 1 (ANXA1), galectin-1 (Gal-1) and galectin-3 (Gal-3) proteins have been identified as important mediators that promote or inhibit leukocyte migration. The expression of these proteins was studied in human neutrophils and endothelial cells (ECs) during a transmigration process induced by IL-8. Upon neutrophil adhesion to EC, a significant increase in the cleaved ANXA1 (LCS3, raised against all ANXA1 isoforms) expression was detected in the plasma membrane of adhered neutrophils and ECs compared to intact ANXA1 isoform (LCPS1, against N-terminus of protein). Adherent neutrophils had elevated Gal-3 levels in the nucleus and cytoplasm, and ECs in their plasma membranes. In contrast, a decrease in the total amounts of Gal-1 was detected in migrated compared to non-migrated neutrophils. Therefore, ANXA1 and Gal-3 changed in their content and localization when neutrophils adhere to endothelia, suggesting a process of sensitive-balance between two endogenous anti- and pro-inflammatory mediators. (c) 2006 International Federation for Cell Biology. Published by Elsevier Ltd. All rights reserved.

Polymeric Nanoparticles as Oral Delivery Systems for Encapsulation and Release of Polyphenolic Compounds: Impact on Quercetin Antioxidant Activity & Bioaccessibility

A delivery system containing polymeric (Eudragit) nanoparticles has been developed for encapsulation and controlled release of bioactive flavonoids (quercetin). Nanoparticles were fabricated using a solvent displacement method. Particle size, morphology, and charge were measured by light scattering, electron microscopy and zeta-potential. Encapsulation efficiency (EE) and release profiles were determined using electrochemical methods. Molecular interactions within the particle matrix were characterized by X-ray diffraction, differential scanning calorimetry, and infrared spectroscopy. Antioxidant properties of free and encapsulated quercetin were analyzed by TBARS and fluorescence spectroscopy. Bioaccessibility of quercetin was evaluated using an in vitro digestion model. Relatively small (d a parts per thousand aEuro parts per thousand 370 nm) anionic polymeric nanoparticles were formed containing quercetin in a non-crystalline form (EE a parts per thousand aEuro parts per thousand 67 %). The main interaction between quercetin and Eudragit was hydrogen bonding. Encapsulated quercetin remained stable during 6 months storage and maintained its antioxidant activity. Quercetin bioaccessibility within simulated small intestinal conditions was improved by encapsulation. The knowledge obtained from this study will facilitate the rational design and fabrication of polymeric nanoparticles as oral delivery systems for encapsulation, protection, and release of bioactive compounds.

Efficient 1535 nm light emission from an all-Si-based optical micro-cavity containing Er3+ and Yb3+ ions

This work reports on the construction and spectroscopic analyses of optical micro-cavities (OMCs) that efficiently emit at ~1535 nm. The emission wavelength matches the third transmission window of commercial optical fibers and the OMCs were entirely based on silicon. The sputtering deposition method was adopted in the preparation of the OMCs, which comprised two Bragg reflectors and one spacer layer made of either Er- or ErYb-doped amorphous silicon nitride. The luminescence signal extracted from the OMCs originated from the 4I13/2→4I15/2 transition (due to Er3+ ions) and its intensity showed to be highly dependent on the presence of Yb3+ ions.According to the results, the Er3+-related light emission was improved by a factor of 48 when combined with Yb3+ ions and inserted in the spacer layer of the OMC. The results also showed the effectiveness of the present experimental approach in producing Si-based light-emitting structures in which the main characteristics are: (a) compatibility with the actual microelectronics industry, (b) the deposition of optical quality layers with accurate composition control, and (c) no need of uncommon elements-compounds nor extensive thermal treatments. Along with the fundamental characteristics of the OMCs, this work also discusses the impact of the Er3+-Yb3+ ion interaction on the emission intensity as well as the potential of the present findings.

EVALUATION OF MAGNESIUM AS A HALL THRUSTER PROPELLANT

In this study, the use of magnesium as a Hall thruster propellant was evaluated. A xenon Hall thruster was modified such that magnesium propellant could be loaded into the anode and use waste heat from the thruster discharge to drive the propellant vaporization. A control scheme was developed, which allowed for precise control of the mass flow rate while still using plasma heating as the main mechanism for evaporation. The thruster anode, which also served as the propellant reservoir, was designed such that the open area was too low for sufficient vapor flow at normal operating temperatures (i.e. plasma heating alone). The remaining heat needed to achieve enough vapor flow to sustain thruster discharge came from a counter-wound resistive heater located behind the anode. The control system has the ability to arrest thermal runaway in a direct evaporation feed system and stabilize the discharge current during voltage-limited operation. A proportional-integral-derivative control algorithm was implemented to enable automated operation of the mass flow control system using the discharge current as the measured variable and the anode heater current as the controlled parameter. Steady-state operation at constant voltage with discharge current excursions less than 0.35 A was demonstrated for 70 min. Using this long-duration method, stable operation was achieved with heater powers as low as 6% of the total discharge power. Using the thermal mass flow control system the thruster operated stably enough and long enough that performance measurements could be obtained and compared to the performance of the thruster using xenon propellant. It was found that when operated with magnesium, the thruster has thrust ranging from 34 mN at 200 V to 39 mN at 300 V with 1.7 mg/s of propellant. It was found to have 27 mN of thrust at 300 V using 1.0 mg/s of propellant. The thrust-to-power ratio ranged from 24 mN/kW at 200 V to 18 mN/kW at 300 volts. The specific impulse was 2000 s at 200 V and upwards of 2700 s at 300 V. The anode efficiency was found to be ~23% using magnesium, which is substantially lower than the 40% anode efficiency of xenon at approximately equivalent molar flow rates. Measurements in the plasma plume of the thruster—operated using magnesium and xenon propellants—were obtained using a Faraday probe to measure off-axis current distribution, a retarding potential analyzer to measure ion energy, and a double Langmuir probe to measure plasma density, electron temperature, and plasma potential. Additionally, the off axis current distributions and ion energy distributions were compared to measurements made in krypton and bismuth plasmas obtained in previous studies of the same thruster. Comparisons showed that magnesium had the largest beam divergence of the four propellants while the others had similar divergence. The comparisons also showed that magnesium and krypton both had very low voltage utilization compared to xenon and bismuth. It is likely that the differences in plume structure are due to the atomic differences between the propellants; the ionization mean free path goes down with increasing atomic mass. Magnesium and krypton have long ionization mean free paths and therefore require physically larger thruster dimensions for efficient thruster operation and would benefit from magnetic shielding.

Diagnostics of classical and dusty plasmas w ith collecting and emissive langmuir probes = Diagnosis de plasmas clásicos y granulares mediante sondas colectoras y emisoras de Langmuir

Las sondas eléctricas se emplean habitualmente en la diagnosis de plasmas. La presente tesis aborda la operación de las sondas colectoras y emisoras de Langmuir en plasmas fríos de baja densidad. El estudio se ha centrado en la determinación del potencial de plasma, Vsp, mediante el potencial flotante de una sonda emisora. Esta técnica consiste en la medida del potencial de la sonda correspondiente a la condición de corriente neta igual a cero, el cual se denomina potencial flotante, VF. Este potencial se desplaza hacia el potencial del plasma según aumenta la emisión termoiónica de la sonda, hasta que se satura cerca de Vsp. Los experimentos llevados a cabo en la pluma de plasma de un motor iónico y en un plasma de descarga de glow muestran que la corriente de electrones termoiónicos es mayor que la corriente de electrones recogidos para una sonda polarizada por debajo del potencial del plasma, resultado inconsistente con la teoría tradicionalmente aceptada. Para investigar estos resultados se ha introducido el parámetro R, definido como el cociente entre la corriente de electrones emitidos y recogidos por la sonda. Este parámetro, que está relacionado con la diferencia de potencial VF - Vsp, también es útil para la descripción de los modos de operación de la sonda emisora (débil, fuerte y más allá del fuerte). Los resultados experimentales evidencian que, al contrario de lo que indica la teoría, R es mayor que la unidad. Esta discrepancia se puede solucionar introduciendo una población efectiva de electrones. Con dicha población, el nuevo modelo para la corriente total de la sonda reproduce los datos experimentales. El origen de este grupo electrónico es todavía una cuestión abierta, pero podría estar originada por una nueva estructura de potencial cerca de la sonda cuando ésta trabaja en el régimen de emisión fuerte. Para explicar dicha estructura de potencial, se propone un modelo unidimensional compuesto por un mínimo de potencial cerca de la superficie de la sonda. El análisis numérico indica que este pozo de potencial aparece para muy altas temperaturas de la sonda, reduciendo la cantidad de electrones emitidos que alcanzan el plasma y evitando así cualquier posible perturbación de éste. Los aspectos experimentales involucrados en el método del potencial flotante también se han estudiado, incluyendo cuestiones como las diferentes técnicas de obtención del VF, el cociente señal-ruido, el acoplamiento de la señal de los equipos utilizados para la obtención de las curvas I-V o la evidencia experimental de los diferentes modos de operación de la sonda. Estas evidencias empíricas se encuentran en todos los aspectos de operación de la sonda: la recolección de electrones, el potencial flotante, la precisión en las curvas I-V y la emisión electrónica. Ésta última también se estudia en la tesis, debido a que un fenómeno de super emisión tiene lugar en el régimen de emisión fuerte. En este modo de operación, las medidas experimentales indican que las corrientes termoiónicas de electrones son mayores que aquéllas predichas por la ecuación de Richardson-Dushman clásica. Por último, la diagnosis de plasmas usando sondas eléctrica bajo presencia de granos de polvo (plasmas granulares) en plasmas fríos de baja densidad también se ha estudiado, mediante la aplicación numérica de la técnica del potencial flotante de la sonda emisora en un plasma no convencional. Los resultados apuntan a que el potencial flotante de una sonda emisora se vería afectado por altas densidades de polvo o grandes partículas. ABSTRACT Electric probes are widely employed for plasma diagnostics. This dissertation concerns the operation of collecting and emissive Langmuir probes in low density cold plasmas. The study is focused on the determination of the plasma potential, Vsp, by means of the floating potential of emissive probes. This technique consists of the measurement of the probe potential, corresponding to the zero net probe current, which is the so-called floating potential, VF . This potential displaces towards the plasma potential as the thermionic electron emission increases, until it saturates near Vsp. Experiments carried out in the plasma plume of an ion thruster and in a glow discharge plasma show the thermionic electron current of the emissive Langmuir probe is higher than the collected electron current, for a probe with a bias potential below Vsp, which is inconsistent with the traditional accepted theory. To investigate these results, a parameter R is introduced as the ratio between the emitted and the collected electron current. This parameter, which is related to the difference VF - Vsp, is also useful for the description of the operation modes of the emissive Langmuir probe (weak, strong and beyond strong). The experimental results give an inconsistency of R > 1, which is solved by a modification of the theory for emissive probes, with the introduction of an effective electron population. With this new electron group, the new model for the total probe current agrees with the experimental data. The origin of this electron group remains an open question, but it might be originated by a new potential structure near the emissive probe when it operates in the strong emission regime. A simple one-dimension model composed by a minimum of potential near the probe surface is discussed for strongly emitting emissive probes. The results indicate that this complex potential structure appears for very high probe temperatures and the potential well might reduce the emitted electrons population reaching the plasma bulk. The experimental issues involved in the floating potential method are also studied, as the different obtaining techniques of VF, the signal-to-noise ratio, the signal coupling of the I-V curve measurement system or the experimental evidence of the probe operation modes. These empirical proofs concern all the probe operation aspects: the electron collection, the floating potential, the I-V curve accuracy as well as the electron emission. This last issue is also investigated in this dissertation, because a super emission takes place in the strong emission regime. In this operation mode, the experimental results indicate that the thermionic electron currents might be higher than those predicted by the classical Richardson-Dushman equation. Finally, plasma diagnosis using electric probes in the presence of dust grains (dusty plasmas) in low density cold plasmas is also addressed. The application of the floating potential technique of the emissive probe in a non-conventional complex plasma is numerically investigated, whose results point out the floating potential of the emissive probe might be shifted for high dust density or large dust particles.

Role of plasma in femtosecond laser pulse propagation

This paper describes physics of nonlinear ultra-short laser pulse propagation affected by plasma created by the pulse itself. Major applications are also discussed. Nonlinear propagation of the femtosecond laser pulses in gaseous and solid transparent dielectric media is a fundamental physical phenomenon in a wide range of important applications such as laser lidars, laser micro-machining (ablation) and microfabrication etc. These applications require very high intensity of the laser field, typically 1013–1015 TW/cm2. Such high intensity leads to significant ionisation and creation of electron-ion or electron-hole plasma. The presence of plasma results into significant multiphoton and plasma absorption and plasma defocusing. Consequently, the propagation effects appear extremely complex and result from competitive counteraction of the above listed effects and Kerr effect, diffraction and dispersion. The theoretical models used for consistent description of laser-plasma interaction during femtosecond laser pulse propagation are derived and discussed. It turns out that the strongly nonlinear effects such self-focusing followed by the pulse splitting are essential. These phenomena feature extremely complex dynamics of both the electromagnetic field and plasma density with different spatio-temporal structures evolving at the same time. Some numerical approaches capable to handle all these complications are also discussed. ©2006 American Institute of Physics

Role of plasma in femtosecond laser pulse propagation

This paper describes physics of nonlinear ultra-short laser pulse propagation affected by plasma created by the pulse itself. Major applications are also discussed. Nonlinear propagation of the femtosecond laser pulses in gaseous and solid transparent dielectric media is a fundamental physical phenomenon in a wide range of important applications such as laser lidars, laser micro-machining (ablation) and microfabrication etc. These applications require very high intensity of the laser field, typically 1013–1015 TW/cm2. Such high intensity leads to significant ionisation and creation of electron-ion or electron-hole plasma. The presence of plasma results into significant multiphoton and plasma absorption and plasma defocusing. Consequently, the propagation effects appear extremely complex and result from competitive counteraction of the above listed effects and Kerr effect, diffraction and dispersion. The theoretical models used for consistent description of laser-plasma interaction during femtosecond laser pulse propagation are derived and discussed. It turns out that the strongly nonlinear effects such self-focusing followed by the pulse splitting are essential. These phenomena feature extremely complex dynamics of both the electromagnetic field and plasma density with different spatio-temporal structures evolving at the same time. Some numerical approaches capable to handle all these complications are also discussed. ©2006 American Institute of Physics

Role of plasma in femtosecond laser pulse propagation

This paper describes physics of nonlinear ultra‐short laser pulse propagation affected by plasma created by the pulse itself. Major applications are also discussed. Nonlinear propagation of the femtosecond laser pulses in gaseous and solid transparent dielectric media is a fundamental physical phenomenon in a wide range of important applications such as laser lidars, laser micro‐machining (ablation) and microfabrication etc. These applications require very high intensity of the laser field, typically 1013–1015 TW/cm2. Such high intensity leads to significant ionisation and creation of electron‐ion or electron‐hole plasma. The presence of plasma results into significant multiphoton and plasma absorption and plasma defocusing. Consequently, the propagation effects appear extremely complex and result from competitive counteraction of the above listed effects and Kerr effect, diffraction and dispersion. The theoretical models used for consistent description of laser‐plasma interaction during femtosecond laser pulse propagation are derived and discussed. It turns out that the strongly nonlinear effects such self‐focusing followed by the pulse splitting are essential. These phenomena feature extremely complex dynamics of both the electromagnetic field and plasma density with different spatio‐temporal structures evolving at the same time. Some numerical approaches capable to handle all these complications are also discussed.

Structural and Electrical Investigation of C 60 –Graphene Vertical Heterostructures

Graphene, with its unique electronic and structural qualities, has become an important playground for studying adsorption and assembly of various materials including organic molecules. Moreover, organic/graphene vertical structures assembled by van der Waals interaction have potential for multifunctional device applications. Here, we investigate structural and electrical properties of vertical heterostructures composed of C60 thin film on graphene. The assembled film structure of C60 on graphene is investigated using transmission electron microscopy, which reveals a uniform morphology of C60 film on graphene with a grain size as large as 500 nm. The strong epitaxial relations between C60 crystal and graphene lattice directions are found, and van der Waals ab initio calculations support the observed phenomena. Moreover, using C60-graphene heterostructures, we fabricate vertical graphene transistors incorporating n-type organic semiconducting materials with an on/off ratio above 3 × 10(3). Our work demonstrates that graphene can serve as an excellent substrate for assembly of molecules, and attained organic/graphene heterostructures have great potential for electronics applications.