Effects of bridge ions, DNA species, and developing temperature on flat-lying DNA monolayers

Recently, we have successfully constructed flat-lying DNA monolayers on a mica surface (J. Phys. Chem. B 2006, 110, 10792-10798). In this work, the effects of various factors including bridge ions, DNA species, and developing temperature on the configuration of DNA monolayers have been investigated by atomic force microscopy (AFM) in detail. AFM results show that the species of bridge ions and developing temperature play a crucial role during the formation process. For example, the divalent cation Zn2+ resulted in many DNA chains stuck side by side in the monolayers due to the strong interactions between it and DNA's bases or the mica surface. Most DNA chain's conglutinations disappeared when the developing temperature was higher than 40 degrees C. Cd2+ and Ca2+ produced more compact DNA monolayers with some obvious aggregations, especially for the DNA monolayers constructed by using Ca2+ as the bridge ion. Co2+ produced well-ordered, flat-lying DNA monolayers similar to that of Mg2+. Furthermore, it was found that the flat-lying DNA monolayers could still form on a mica surface when plasmid DNA pBR 322 and linear DNA pBR 322/Pst I were used as the DNA source. Whereas, it was hard to form DNA monolayers on a (3-aminopropyl)triethoxysilane-mica surface because the strong interactions between DNA and substrate prevented the lateral movement of DNA molecules.

Modulating unimolecular charge transfer by exciting bridge vibrations.

Ultrafast UV-vibrational spectroscopy was used to investigate how vibrational excitation of the bridge changes photoinduced electron transfer between donor (dimethylaniline) and acceptor (anthracene) moieties bridged by a guanosine-cytidine base pair (GC). The charge-separated (CS) state yield is found to be lowered by high-frequency bridge mode excitation. The effect is linked to a dynamic modulation of the donor-acceptor coupling interaction by weakening of H-bonding and/or by disruption of the bridging base-pair planarity.

The Evolution of the Russian Romance Through the Nineteenth and Twentieth centuries

This performance dissertation traced the evolution of the Russian romance from 1800 to the present. The Russian romance is a relatively unknown and greatly neglected genre of classical art songs. It is commonly believed that the Russian romance began with Dargomizhsky and Glinka proceeding directly to Tchaikovsky and Rachmaninoff. Forgotten are the composers before Dargornizhsky and Glinka, the bridge composers, and the post-Tchaikovsky and post-Rachmaninoff composers. This may be, in part, because of the difficulties in obtaining Russian vocal scores. While most of the musical world is acquainted with the magnificent Russian instrumental music, the "true soul" of the Russian people lies in its romances. I presented examples of the two different schools of composition, reflecting their philosophical differences in thinking that came about in the 1860s: (1) Russian National school, (2) Western European school. Each school's influence on generations of Russian composers and their pupils have been represented in the recital programs. Also represented was the effect of the October Revolution on music and the voice of the Russian people, Anna Akhmatova. The amount of music that could be included in this dissertation greatly exceeds the amount of available performance time and represents a selected portion of the repertoire. The first recital included repertoire from the beginning of the romance in the early nineteenth century to the beginning of the twentieth century and the second recital focused on the music of the twentieth century, pre and post, the October Revolution. Finally, given the status of Anna Akhmatova and her contributions, the third recital was devoted entirely to her poetry. The "Russian soul" is one of deep, heartfelt emotions and sorrow. Happiness and joy are also present, but always with a touch of melancholy. The audience did not simply go through a musical journey, but took a journey through the "Russian soul". With the strong response of the audience to these recitals, my belief that this repertoire deserves a prominent place in recital programming was confirmed.

Evaporation-induced evolution of the capillary force between two grains

© 2014, Springer-Verlag Berlin Heidelberg.The evolution of capillary forces during evaporation and the corresponding changes in the geometrical characteristics of liquid (water) bridges between two glass spheres with constant separation are examined experimentally. For comparison, the liquid bridges were also tested for mechanical extension (at constant volume). The obtained results reveal substantial differences between the evolution of capillary force due to evaporation and the evolution due to extension of the liquid bridges. During both evaporation and extension, the change of interparticle capillary forces consists in a force decrease to zero either gradually or via rupture of the bridge. At small separations between the grains (short & wide bridges) during evaporation and at large volumes during extension, there is a slight initial increase of force. During evaporation, the capillary force decreases slowly at the beginning of the process and quickly at the end of the process; during extension, the capillary force decreases quickly at the beginning and slowly at the end of the process. Rupture during evaporation of the bridges occurs most abruptly for bridges with wider separations (tall and thin), sometimes occurring after only 25% of the water volume was evaporated. The evolution (pinning/depinning) of two geometrical characteristics of the bridge, the diameter of the three-phase contact line and the “apparent” contact angle at the solid/liquid/gas interface, seem to control the capillary force evolution. The findings are of relevance to the mechanics of unsaturated granular media in the final phase of drying.

General insight into CO oxidation: A density functional theory study of the reaction mechanism on platinum oxides

CO oxidation on PtO2(110) has been studied using density functional theory calculations. Four possible reaction mechanisms were investigated and the most feasible one is the following: (i) the O at the bridge site of PtO2(110) reacts with CO on the coordinatively unsaturated site (CUS) with a negligible barrier; (ii) O-2 adsorbs on the bridge site and then interacts with CO on the CUS to form an OO-CO complex; (iii) the bond of O-OCO breaks to produce CO2 with a small barrier (0.01 eV). The CO oxidation mechanisms on metals and metal oxides are rationalized by a simple model: The O-surface bonding determines the reactivity on surfaces; it also determines whether the atomic or molecular mechanism is preferred. The reactivity on metal oxides is further found to be related to the 3rd ionization energy of the metal atom.

Catalytic role of gold in gold-based catalysts: A density functional theory study on the CO oxidation on gold

Gold-based catalysts have been of intense interests in recent years, being regarded as a new generation of catalysts due to their unusually high catalytic performance. For example, CO oxidation on Au/TiO2 has been found to occur at a temperature as low as 200 K. Despite extensive studies in the field, the microscopic mechanism of CO oxidation on Au-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Au, we have performed extensive density functional theory calculations for the elementary steps in CO oxidation on Au surfaces. O atom adsorption, CO adsorption, O-2 dissociation, and CO oxidation on a series of Au surfaces, including flat surfaces, defects and small clusters, have been investigated in detail. Many transition states involved are located, and the lowest energy pathways are determined. We find the following: (i) the most stable site for O atom on Au is the bridge site of step edge, not a kink site; (ii) O-2 dissociation on Au (O-2-->20(ad)) is hindered by high barriers with the lowest barrier being 0.93 eV on a step edge; (iii) CO can react with atomic O with a substantially lower barrier, 0.25 eV, on Au steps where CO can adsorb; (iv) CO can react with molecular O-2 on Au steps with a low barrier of 0.46 eV, which features an unsymmetrical four-center intermediate state (O-O-CO); and (v) O-2 can adsorb on the interface of Au/TiO2 with a reasonable chemisorption energy. On the basis of our calculations, we suggest that (i) O-2 dissociation on Au surfaces including particles cannot occur at low temperatures; (ii) CO oxidation on Au/inactive-materials occurs on Au steps via a two-step mechanism: CO+O-2-->CO2+O, and CO+O-->CO2; and (iii) CO oxidation on Au/active-materials also follows the two-step mechanism with reactions occurring at the interface.

A density functional theory study of the reaction of C+O, C+N, and C+H on close packed metal surfaces

Density functional theory (DFT) has been used to determine reaction pathways for several reactions taking place on Pt(111) and Cu(111) surfaces. On Pt(111), the reactions of C+O and C+N were studied, and on Cu(111) we investigated the reaction of C+H. The structures of the transition states accessed in each reaction are similar. An equivalent distance separates the reactants with the first located at a three-fold hollow site and the second close to a bridge site. Previous DFT studies have, in fact, often identified transition states of this type and in every case it is the reactant with the weaker chemisorption energy that is located close to the bridge site. An explanation as to why this is so is provided. (C) 2001 American Institute of Physics.

Finite element investigation of the structural behaviour of deck slabs in composite bridges

This research studies the structural behaviour of bridge deck slabs under static patch loads in steel–concrete composite bridges and investigates compressive membrane action (CMA) in concrete bridge decks slabs, which governs the structural behaviour. A non-linear 3D finite element analysis models was developed using ABAQUS 6.5 software packages. Experimental data from one-span composite bridge structures are used to validate and calibrate the proposed FEM models. A series of parametric studies is conducted. The analysis results are discussed and conclusions on the behaviour of the bridge decks are presented.

Monitoring and repair of an impact damaged prestressed bridge

This paper details the monitoring and repair of an impact damaged prestressed concrete bridge. The repair was required following an impact from a low-loader carrying an excavator while passing underneath the bridge. The repair was carried out by preloading the bridge in the vicinity of the damage to relieve some prestressing. This preload was removed following the hardening and considerable strength gain of the repair material. The true behaviour of damaged prestressed concrete bridges during repair is difficult to estimate theoretically due to lack of benchmarking and inadequacy of assumed damage models. A network of strain gauges at locations of interest was thus installed during the entire period of repair. Effects of various activities were qualitatively and quantitatively observed. The interaction and rapid, model-free calibration of damaged and undamaged beams, including identification of damaged gauges were also probed. This full scale experiment is expected to be of interest and benefit to the practising engineer and the researcher alike.

The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

2-Phosphanylethylcyclopentadienyl lithium compounds, Li[C5R'(4)(CH2)(2)PR2] (R = Et, R' = H or Me, R = Ph, R' = Me), have been prepared from the reaction of spirohydrocarbons C5R'(4)(C2H4) with LiPR2. C5Et4HSiMe2CH2PMe2, was prepared from reaction of Li[C5Et4] with Me2SiCl2 followed by Me2PCH2Li. The lithium salts were reacted with [RhCl(CO)2]2,[IrCl(CO)3] or [Co-2(CO)(8)] to give [M(C5R'(4)(CH2) 2PR2)(CO)] (M = Rh, R = Et, R' = H or Me, R= Ph, R' = Me; M = Ir or Co, R = Et, R' = Me), which have been fully characterised, in many cases crystallographically as monomers with coordination of the phosphorus atom and the cyclopentadienyl ring. The values of nu(CO) for these complexes are usually lower than those for the analogous complexes without the bridge between the cyclopentadienyl ring and the phosphine, the exception being [Rh(Cp'(CH2)(2)PEt2)(CO)] (Cp' = C5Me4), the most electron rich of the complexes. [Rh(C5Et4SiMe2CH2PMe2)(CO)] may be a dimer. [Co-2(CO)(8)] reacts with C5H5(CH2)(2)PEt2 or C5Et4HSiMe2CH2PMe2 (L) to give binuclear complexes of the form [Co-2(CO)(6)L-2] with almost linear PCoCoP skeletons. [Rh(Cp'(CH2)(2)PEt2)(CO)] and [Rh(Cp'(CH2)(2)PPh2)(CO)] are active for methanol carbonylation at 150 degrees C and 27 bar CO, with the rate using [Rh(Cp'(CH2)(2)PPh2)(CO)] (0.81 mol dm(-3) h(-1)) being higher than that for [RhI2(CO)(2)](-) (0.64 mol dm(-3) h(-1)). The most electron rich complex, [Rh(Cp'(CH2)(2)PEt2)(CO)] (0.38 mol dm(-3) h(-1)) gave a comparable rate to [Cp*Rh(PEt3)(CO)] (0.30 mol dm(-3) h(-1)), which was unstable towards oxidation of the phosphine. [Rh(Cp'(CH2)(2)PEt2)I-2], which is inactive for methanol carbonylation, was isolated after the methanol carbonylation reaction using [Rh(Cp'(CH2)(2)PEt2)(CO)].

A wavelet-based damage detection algorithm based on bridge acceleration response to a vehicle

Previous research based on theoretical simulations has shown the potential of the wavelet transform to detect damage in a beam by analysing the time-deflection response due to a constant moving load. However, its application to identify damage from the response of a bridge to a vehicle raises a number of questions. Firstly, it may be difficult to record the difference in the deflection signal between a healthy and a slightly damaged structure to the required level of accuracy and high scanning frequencies in the field. Secondly, the bridge is going to have a road profile and it will be loaded by a sprung vehicle and time-varying forces rather than a constant load. Therefore, an algorithm based on a plot of wavelet coefficients versus time to detect damage (a singularity in the plot) appears to be very sensitive to noise. This paper addresses these questions by: (a) using the acceleration signal, instead of the deflection signal, (b) employing a vehicle-bridge finite element interaction model, and (c) developing a novel wavelet-based approach using wavelet energy content at each bridge section which proves to be more sensitive to damage than a wavelet coefficient line plot at a given scale as employed by others.

A bridge-monitoring tool based on bridge and vehicle accelerations

Previous research on damage detection based on the response of a structure to a moving load has reported decay in accuracy with increasing load speed. Using a 3D vehicle – bridge interaction model, this paper shows that the area under the filtered acceleration response of the bridge increases with increasing damage, even at highway load speeds. Once a datum reading is established, the area under subsequent readings can be monitored and compared with the baseline reading, if an increase is observed it may indicate the presence of damage. The sensitivity of the proposed approach to road roughness and noise is tested in several damage scenarios. The possibility of identifying damage in the bridge by analysing the acceleration response of the vehicle traversing it is also investigated. While vehicle acceleration is shown to be more sensitive to road roughness and noise and therefore less reliable than direct bridge measurements, damage is successfully identified in favourable scenarios.

Changes in modal parameters of a steel truss bridge due to artificial damage

This study investigated how damage changes the modal parameters of a real bridge by means of a field experiment which was conducted on a real steel truss bridge consecutively subjected to four artificial damage scenarios. In the experiment, both the forced and free vibrations of the bridge were recorded, the former for identifying higher modes available exclusively and the latter for lower modes with higher resolution. Results show that modal parameters are little affected by damage causing low stress redistribution. Modal frequencies decrease as damage causing high stress redistribution is applied; such a change can be observed if the damage is at the non-nodal point of the corresponding mode shape. Mode shapes are distorted due to asymmetric damage; they show an amplification in the damaged side as damage is applied at the non-nodal point. Torsion modes become more dominant as damage is applied either asymmetrically or on an element against large design loads. © 2013 Taylor & Francis Group, London.

Identification of damping in a bridge using a moving instrumented vehicle

In recent years, there has been a significant increase in the number of bridges which are being instrumented and monitored on an ongoing basis. This is in part due to the introduction of bridge management systems designed to provide a high level of protection to the public and early warning if the bridge becomes unsafe. This paper investigates a novel alternative; a low-cost method consisting of the use of a vehicle fitted with accelerometers on its axles to monitor the dynamic behaviour of bridges. A simplified half-car vehicle-bridge interaction model is used in theoretical simulations to test the effectiveness of the approach in identifying the damping ratio of the bridge. The method is tested for a range of bridge spans and vehicle velocities using theoretical simulations and the influences of road roughness, initial vibratory condition of the vehicle, signal noise, modelling errors and frequency matching on the accuracy of the results are investigated.

Wavelet Based Damage Detection Approach for Bridge Structures Utilising Vehicle Vibration

This paper investigates a wavelet-based damage detection approach for bridge structures. By analysing the continuous wavelet transform of the vehicle response, the approach aims to identify changes in the bridge response which may indicate the existence of damage. A numerical vehicle-bridge interaction model is used in simulations as part of a sensitivity study. Furthermore, a laboratory experiment is carried out to investigate the effects of varying vehicle configuration, speed and bridge damping on the ability of the vehicle to detect changes in the bridge response. The accelerations of the vehicle and bridge are processed using a continuous wavelet transform, allowing time-frequency analysis to be carried out on the responses of the laboratory vehicle-bridge interaction system. Results indicate the most favourable conditions for successful implementation of the approach.