Wavelength dependence of light-induced domain nucleation in MgO-doped congruent LiNbO3 crystal

Within the wavelength range from 351 to 799 nm, the different reductions of nucleation field induced by the focused continuous laser irradiation are achieved in the 5 mol % MgO-doped congruent LiNbO3 crystals. The reduction proportion increases exponentially with decreasing irradiation wavelength and decreases exponentially with increasing irradiation wavelength. At one given wavelength, the reduction proportion increases exponentially with increasing irradiation intensity. An assumption is proposed that the reduction of nucleation field is directly related to the defect structure of crystal lattice generated by the complex coaction of incident irradiation field and external electric field. (c) 2007 American Institute of Physics.

Electron-beam-induced direct etching of graphene

We present electron-beam-induced oxidation of single- and bilayer graphene devices in a low-voltage scanning electron microscope. We show that the injection of oxygen leads to targeted etching at the focal point, enabling us to pattern graphene with a resolution of better than 20 nm. Voltage-contrast imaging, in conjunction with finite-element simulations, explain the secondary-electron intensities and correlate them to the etch profile. © 2013 Elsevier Ltd. All rights reserved.

Modelling of settlement induced building damage

This thesis focuses on the modelling of settlement induced damage to masonry buildings. In densely populated areas, the need for new space is nowadays producing a rapid increment of underground excavations. Due to the construction of new metro lines, tunnelling activity in urban areas is growing. One of the consequences is a greater attention to the risk of damage on existing structures. Thus, the assessment of potential damage of surface buildings has become an essential stage in the excavation projects in urban areas (Chapter 1). The current damage risk assessment procedure is based on strong simplifications, which not always lead to conservative results. Object of this thesis is the development of an improved damage classification system, which takes into account the parameters influencing the structural response to settlement, like the non-linear behaviour of masonry and the soil-structure interaction. The methodology used in this research is based on experimental and numerical modelling. The design and execution of an experimental benchmark test representative of the problem allows to identify the principal factors and mechanisms involved. The numerical simulations enable to generalize the results to a broader range of physical scenarios. The methodological choice is based on a critical review of the currently available procedures for the assessment of settlement-induced building damage (Chapter 2). A new experimental test on a 1/10th masonry façade with a rubber base interface is specifically designed to investigate the effect of soil-structure interaction on the tunnelling-induced damage (Chapter 3). The experimental results are used to validate a 2D semi-coupled finite element model for the simulation of the structural response (Chapter 4). The numerical approach, which includes a continuum cracking model for the masonry and a non-linear interface to simulate the soil-structure interaction, is then used to perform a sensitivity study on the effect of openings, material properties, initial damage, initial conditions, normal and shear behaviour of the base interface and applied settlement profile (Chapter 5). The results assess quantitatively the major role played by the normal stiffness of the soil-structure interaction and by the material parameters defining the quasi-brittle masonry behaviour. The limitation of the 2D modelling approach in simulating the progressive 3D displacement field induced by the excavation and the consequent torsional response of the building are overcome by the development of a 3D coupled model of building, foundation, soil and tunnel (Chapter 6). Following the same method applied to the 2D semi-coupled approach, the 3D model is validated through comparison with the monitoring data of a literature case study. The model is then used to carry out a series of parametric analyses on geometrical factors: the aspect ratio of horizontal building dimensions with respect to the tunnel axis direction, the presence of adjacent structures and the position and alignment of the building with respect to the excavation (Chapter 7). The results show the governing effect of the 3D building response, proving the relevance of 3D modelling. Finally, the results from the 2D and 3D parametric analyses are used to set the framework of an overall damage model which correlates the analysed structural features with the risk for the building of being damaged by a certain settlement (Chapter 8). This research therefore provides an increased experimental and numerical understanding of the building response to excavation-induced settlements, and sets the basis for an operational tool for the risk assessment of structural damage (Chapter 9).

Effects of external magnetic field on the effective g factor of (Ga,Mn)As

With the help of time resolved magneto-optic Kerr rotation measurements, the optically induced spin precession in heavily doped diluted magnetic semiconductor Ga0.937Mn0.063 As was observed. It was found that the effective g factor increases with increasing magnetic field, which is attributed to the magnetic-field-induced increase of the density of the non-localized holes. Those free holes will couple with the localized magnetic ions by p-d interactions, leading to the formation of spontaneous magnetization in Ga0.937Mn0.063As, which in turn to the enhancement of the effective g factor.

Surface-enhanced resonance Raman spectroscopy and spectroscopy study of redox-induced conformational equilibrium of cytochrome c adsorbed on DNA-modified metal electrode

The redox-induced conformational equilibrium of cytochrome c (cyt c) adsorbed on DNA-modified metal electrode and the interaction mechanism of DNA with cyt c have been studied by electrochemical, spectroscopic and spectroelectrochemical techniques. The results indicate that the external electric field induces potential-dependent coordination equilibrium of the adsorbed cyt c between its oxidized state (with native six-coordinate low-spin and non-native five-coordinate high-spin heme configuration) and its reduced state (with native six-coordinate low-spin heme configuration) on DNA-modified metal electrode. The strong interactions between DNA and cyt c induce the self-aggregation of cyt c adsorbed on DNA. The orientational distribution of cyt c adsorbed on DNA-modified metal electrode is potential-dependent, which results in the deviation from an ideal Nernstian behavior of the adsorbed cyt c at high electrode potentials. The electric-field-induced increase in the activation barrier of proton-transfer steps attributed to the rearrangement of the hydrogen bond network and the self-aggregation of cyt c upon adsorption on DNA-modified electrode strongly decrease the interfacial electron transfer rate.

Ferrofluid thin films as optical gaussmeters proposed for field and magnetic moment sensing

Ferrofluids belonging to the series, Ni x Fe1-x Fe2O4 and Zn x Fe1-x Fe2O4, were synthesized using cold co-precipitation. Liquid films of these ferrofluids were prepared by encapsulating the ferrofluids in between two optically smooth and ultrasonically cleaned glass plates. Magnetic field induced laser transmission through these ferrofluid films has been investigated. Magnetic field values can be calibrated in terms of output laser power in the low field region in which the variation is linear. This set up can be used as a cheap optical gaussmeter in the low field regime. Using the same set-up, the saturation magnetization of the sample used can also be calculated with a sample that is pre-characterized. Hence both magnetization of the sample, as well as applied magnetic field can be sensed and calculated with a precalibrated sample.

Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations

In the finite field (FF) treatment of vibrational polarizabilities and hyperpolarizabilities, the field-free Eckart conditions must be enforced in order to prevent molecular reorientation during geometry optimization. These conditions are implemented for the first time. Our procedure facilities identification of field-induced internal coordinates that make the major contribution to the vibrational properties. Using only two of these coordinates, quantitative accuracy for nuclear relaxation polarizabilities and hyperpolarizabilities is achieved in π-conjugated systems. From these two coordinates a single most efficient natural conjugation coordinate (NCC) can be extracted. The limitations of this one coordinate approach are discussed. It is shown that the Eckart conditions can lead to an isotope effect that is comparable to the isotope effect on zero-point vibrational averaging, but with a different mass-dependence

Heme-induced biomarkers associated with red meat promotion of colon cancer are not modulated by the intake of nitrite

Red and processed meat consumption is associated with the risk of colorectal cancer. Three hypotheses are proposed to explain this association, via heme-induced oxidation of fat, heterocyclic amines, or N-nitroso compounds. Rats have often been used to study these hypotheses, but the lack of enterosalivary cycle of nitrate in rats casts doubt on the relevance of this animal model to predict nitroso- and heme-associated human colon carcinogenesis. The present study was thus designed to clarify whether a nitrite intake that mimics the enterosalivary cycle can modulate hemeinduced nitrosation and fat peroxidation. This study shows that, in contrast with the starting hypothesis, drinking water added with nitrite to mimic the salivary nitrite content did not change the effect of hemoglobin on biochemicalmarkers linked to colon carcinogenesis, notably lipid peroxidation and cytotoxic activity in the colon of rat. However, ingested sodium nitrite increased fecal nitrosocompounds level, but their fecal concentration and their nature (iron-nitrosyl) would probably not be associated with an increased risk of cancer.We thus suggest that the rat model could be relevant for study the effect of red meat on colon carcinogenesis, in spite of the lack of nitrite in the saliva of rats.

An improved three-dimensional model for growth of oxide films induced by laser heating

In this paper we consider a three-dimensional heat diffusion model to explain the growth of oxide films which takes place when a laser beam is shined on and heats a metallic layer deposited on a glass substrate in a normal atmospheric environment. In particular, we apply this model to the experimental results obtained for the dependence of the oxide layer thickness on the laser density power for growth of TiO2 films grown on Ti-covered glass slides. We show that there is a very good agreement between the experimental results and the theoretical predictions from our proposed three-dimensional model, improving the results obtained with the one-dimensional heat diffusion model previously reported. Our theoretical results also show the occurrence of surface cooling between consecutive laser pulses, and that the oxide track surface profile closely follows the spatial laser profile indicating that heat diffusive effects can be neglected in the growth of oxide films by laser heating. © 2001 Elsevier Science B.V.

Femtosecond laser induced synthesis of Au nanoparticles mediated by chitosan

This paper reports the synthesis of Au nanoparticles by 30-fs pulses irradiation of a sample containing HAuCl4 and chitosan, a biopolymer used as reducing agent and stabilizer. We observed that it is a multi-photon induced process, with a threshold irradiance of 3.8 x 10(11) W/cm(2) at 790 nm. By transmission electron microscopy we observed nanoparticles from 8 to 50 nm with distinct shapes. Infrared spectroscopy indicated that the reduction of gold and consequent production of nanoparticles is related to the fs-pulse induced oxidation of hydroxyl to carbonyl groups in chitosan. (C) 2011 Optical Society of America

Oxidation of 3-hydroxyanthranilic acid to the phenoxazinone cinnabarinic acid by peroxyl radicals and by compound I of peroxidases or catalase

Since 3-hydroxyanthranilic acid (3HAA), an oxidation product of tryptophan metabolism, is a powerful radical scavenger [Christen, S., Peterhans, E., ; Stocker, R. (1990) Proc. Natl. Acad. Sci. U.S.A. 87, 2506], its reaction with peroxyl radicals was investigated further. Exposure to aqueous peroxyl radicals generated at constant rate under air from the thermolabile radical initiator 2,2'-azobis[2-amid-inopropane] hydrochloride (AAPH) resulted in rapid consumption of 3HAA with initial accumulation of its cyclic dimer, cinnabarinic acid (CA). The initial rate of formation of the phenoxazinone CA accounted for approximately 75% of the initial rate of oxidation of 3HAA, taking into account that 2 mol of 3HAA are required to form 1 mol of CA. Consumption of 3HAA under anaerobic conditions (where alkyl radicals are produced from AAPH) was considerably slower and did not result in detectable formation of CA. Addition of superoxide dismutase enhanced autoxidation of 3HAA as well as the initial rates of peroxyl radical-induced oxidation of 3HAA and formation of CA by approximately 40-50%, whereas inclusion of xanthine/xanthine oxidase decreased the rate of oxidation of 3HAA by approximately 50% and inhibited formation of CA almost completely, suggesting that superoxide anion radical (O2.-) was formed and reacted with reaction intermediate(s) to curtail formation of CA. Formation of CA was also observed when 3HAA was added to performed compound I of horseradish peroxidase (HRPO) or catalytic amounts of either HRPO, myeloperoxidase, or bovine liver catalase together with glucose/glucose oxidase.(ABSTRACT TRUNCATED AT 250 WORDS)

Effect of external electric field on hydrogen adsorption over activated carbon separated by dielectric materials

Energy crisis and worldwide environmental problem make hydrogen a prospective energy carrier. However, storage and transportation of hydrogen in large quantities at small volume is currently not practical. Lots of materials and devices have been developed for storage hydrogen, but to today none is able to meet the DOE targets. Activated carbon has been found to be a good hydrogen adsorbent due to its high surface area. However, the weak van der Waals force between hydrogen and the adsorbent has limited the adsorption capacity. Previous studies have found that enhanced adsorption can be obtained with applied electric field. Stronger interaction between the polarized hydrogen and the charged sorbents under high voltage is considered as the reason. This study was initiated to investigate if the adsorption can be further enhanced when the activated carbon particles are separated with a dielectric coating. Dielectric TiO2 nanoparticles were first utilized. Hydrogen adsorption measurements on the TiO2-coated carbon materials, with or without an external electric field, were made. The results showed that the adsorption capacity enhancement increased with the increasing amount of TiO2 nanoparticles with an applied electric field. Since the hydrogen adsorption capacity on TiO2 particles is very low and there is no hydrogen adsorption enhancement on TiO2 particles alone when electric field is applied, the effect of dielectric coating is demonstrated. Another set of experiments investigated the behavior of hydrogen adsorption over TiO2-coated activated carbon under various electric potentials. The results revealed that the hydrogen adsorption first increased and then decreased with the increase of electric field. The improved storage was due to a stronger interaction between charged carbon surface and polarized hydrogen molecule caused by field induced polarization of TiO2 coating. When the electric field was sufficient to cause considerable ionization of hydrogen, the decrease of hydrogen adsorption occurred. The current leak detected at 3000 V was a sign of ionization of hydrogen. Experiments were also carried out to examine the hydrogen adsorption performances over activated carbon separated by other dielectric materials, MgO, ZnO and BaTiO3, respectively. For the samples partitioned with MgO and ZnO, the measurements with and without an electric field indicated negligible differences. Electric field enhanced adsorption has been observed on the activated carbon separated with BaTiO3, a material with unusually high dielectric constant. Corresponding computational calculations using Density Functional Theory have been performed on hydrogen interaction with charged TiO2 molecule as well as TiO2 molecule, coronene and TiO2-doped coronene in the presence of an electric field. The simulated results were consistent with the observations from experiments, further confirming the proposed hypotheses.

A Compact Tetrathiafulvalene-Benzothiadiazole Dyad and Its Highly Symmetrical Charge-Transfer Salt: Ordered Donor π-Stacks Closely Bound to Their Acceptors

A compact and planar donor–acceptor molecule 1 comprising tetrathiafulvalene (TTF) and benzothiadiazole (BTD) units has been synthesised and experimentally characterised by structural, optical, and electrochemical methods. Solution-processed and thermally evaporated thin films of 1 have also been explored as active materials in organic field-effect transistors (OFETs). For these devices, hole field-effect mobilities of μFE=(1.3±0.5)×10−3 and (2.7±0.4)×10−3 cm2 V s−1 were determined for the solution-processed and thermally evaporated thin films, respectively. An intense intramolecular charge-transfer (ICT) transition at around 495 nm dominates the optical absorption spectrum of the neutral dyad, which also shows a weak emission from its ICT state. The iodine-induced oxidation of 1 leads to a partially oxidised crystalline charge-transfer (CT) salt {(1)2I3}, and eventually also to a fully oxidised compound {1I3}⋅1/2I2. Single crystals of the former CT compound, exhibiting a highly symmetrical crystal structure, reveal a fairly good room temperature electrical conductivity of the order of 2 S cm−1. The one-dimensional spin system bears compactly bonded BTD acceptors (spatial localisation of the LUMO) along its ridge.

A magneto-mineralogical study of basalt at DSDP Leg 73 Holes

The basalts in Holes 519A, 522B, and 524 were studied for intensity of natural remanent magnetization, magnetic hysteresis, magnetic susceptibility, stability of isothermal remanence, and thermomagnetic behavior. Some of these properties are sensitive to both the composition and the microstructure of the magnetic minerals, others to composition only. Thus it is possible to separate the two effects and to trace the variation of effective magnetic grain size and degree of alteration within a lithologic unit or over a yet larger distance or time interval. The flow in Hole 519A is highly maghemitized at the top, the degree of maghemitization decreasing with depth in the flow. Effective grain size increases with increasing depth. Electron microprobe analysis of the titanomaghemite grains in these samples provides no support for the leaching out of iron during alteration. The pillows and flows in Hole 522B are distributed among a number of cooling units, and no systematic downhole variations are apparent. The inferred magneto-petrology is consistent with the cooling and alteration history that might be expected within the units. The upper and lower sills in Hole 524 are more uniform and have a larger concentration of well-developed magnetic mineral grains than the pillows and flows in Holes 519A and 522B. Maghemitization appears to have developed from the boundaries of the sills that are in contact with the sediments between the sills.

Electrostatic plasma instabilities excited by a high‐frequency electric field

The electrostatic plasma waves excited by a uniform, alternating electric field of arbitrary intensity are studied on the basis of the Vlasov equation; their dispersion relation, which involves the determinant of either of two infinite matrices, is derived. For ω0 ≫ ωpi (ω0 being the applied frequency and ωpi the ion plasma frequency) the waves may be classified in two groups, each satisfying a simple condition; this allows writing the dispersion relation in closed form. Both groups coalesce (resonance) if (a) ω0  ≈  ωpe/r (r any integer) and (b) the wavenumber k is small. A nonoscillatory instability is found; its distinction from the DuBois‐Goldman instability and its physical origin are discussed. Conditions for its excitation (in particular, upper limits to ω0,k, and k⋅vE,vE being the field‐induced electron velocity), and simple equations for the growth rate are given off‐resonance and at ω0  ≈  ωpi. The dependence of both threshold and maximum growth rate on various parameters is discussed, and the results are compared with those of Silin and Nishikawa. The threshold at ω0  ≈  ωpi/r,r  ≠  1, is studied.