Search results for: displacement-type excitation

Authors: S. Raja, K. M. Parammasivam, V. Aghilesh

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Fluid-structure interaction is a crucial consideration in the design of many engineering systems such as flight vehicles and bridges. Aircraft lifting surfaces and turbine blades can fail due to oscillations caused by fluid-structure interaction. Hence, it is focussed to study the fluid-structure interaction in the present research. First, the effect of free vibration over the panel is studied. It is well known that the deformation of a panel and flow induced forces affects one another. The selected panel has a span 300mm, chord 300mm and thickness 2 mm. The project is to study, the effect of cross-sectional area and the stiffener location is carried out for the same panel. The stiffener spacing is varied along both the chordwise and span-wise direction. Then for that optimal location the ideal stiffener length is identified. The effect of stiffener cross-section shapes (T, I, Hat, Z) over flutter velocity has been conducted. The flutter velocities of the selected panel with two rectangular stiffeners of cantilever configuration are estimated using MSC NASTRAN software package. As the flow passes over the panel, deformation takes place which further changes the flow structure over it. With increasing velocity, the deformation goes on increasing, but the stiffness of the system tries to dampen the excitation and maintain equilibrium. But beyond a critical velocity, the system damping suddenly becomes ineffective, so it loses its equilibrium. This estimated in NASTRAN using PK method. The first 10 modal frequencies of a simple panel and stiffened panel are estimated numerically and are validated with open literature. A grid independence study is also carried out and the modal frequency values remain the same for element lengths less than 20 mm. The current investigation concludes that the span-wise stiffener placement is more effective than the chord-wise placement. The maximum flutter velocity achieved for chord-wise placement is 204 m/s while for a span-wise arrangement it is augmented to 963 m/s for the stiffeners location of ¼ and ¾ of the chord from the panel edge (50% of chord from either side of the mid-chord line). The flutter velocity is directly proportional to the stiffener cross-sectional area. A significant increment in flutter velocity from 218m/s to 1024m/s is observed for the stiffener lengths varying from 50% to 60% of the span. The maximum flutter velocity above Mach 3 is achieved. It is also observed that for a stiffened panel, the full effect of stiffener can be achieved only when the stiffener end is clamped. Stiffeners with Z cross section incremented the flutter velocity from 142m/s (Panel with no stiffener) to 328 m/s, which is 2.3 times that of simple panel.

Keywords: stiffener placement, stiffener cross-sectional area, stiffener length, stiffener cross sectional area shape

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Authors: Carlos Teodoro, Oscar Bautista

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In this work, we analyze theoretically the mass transport in a time-periodic electroosmotic flow through a parallel flat plate microchannel under different periodic functions of the applied external electric field. The microchannel connects two reservoirs having different constant concentrations of an electro-neutral solute, and the zeta potential of the microchannel walls are assumed to be uniform. The governing equations that allow determining the mass transport in the microchannel are given by the Poisson-Boltzmann equation, the modified Navier-Stokes equations, where the Debye-Hückel approximation is considered (the zeta potential is less than 25 mV), and the species conservation. These equations are nondimensionalized and four dimensionless parameters appear which control the mass transport phenomenon. In this sense, these parameters are an angular Reynolds, the Schmidt and the Péclet numbers, and an electrokinetic parameter representing the ratio of the half-height of the microchannel to the Debye length. To solve the mathematical model, first, the electric potential is determined from the Poisson-Boltzmann equation, which allows determining the electric force for various periodic functions of the external electric field expressed as Fourier series. In particular, three different excitation wave forms of the external electric field are assumed, a) sawteeth, b) step, and c) a periodic irregular functions. The periodic electric forces are substituted in the modified Navier-Stokes equations, and the hydrodynamic field is derived for each case of the electric force. From the obtained velocity fields, the species conservation equation is solved and the concentration fields are found. Numerical calculations were done by considering several binary systems where two dilute species are transported in the presence of a carrier. It is observed that there are different angular frequencies of the imposed external electric signal where the total mass transport of each species is the same, independently of the molecular diffusion coefficient. These frequencies are called crossover frequencies and are obtained graphically at the intersection when the total mass transport is plotted against the imposed frequency. The crossover frequencies are different depending on the Schmidt number, the electrokinetic parameter, the angular Reynolds number, and on the type of signal of the external electric field. It is demonstrated that the mass transport through the microchannel is strongly dependent on the modulation frequency of the applied particular alternating electric field. Possible extensions of the analysis to more complicated pulsation profiles are also outlined.

Keywords: electroosmotic flow, mass transport, oscillatory flow, species separation

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Authors: Laura Micheli, Majd Hijazi, Mahmoud Faytarouni

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The damage reported by oil and gas industrial facilities revealed the utmost vulnerability of steel liquid storage tanks to seismic events. The failure of steel storage tanks may yield devastating and long-lasting consequences on built and natural environments, including the release of hazardous substances, uncontrolled fires, and soil contamination with hazardous materials. It is, therefore, fundamental to reliably predict the damage that steel liquid storage tanks will likely experience under future seismic hazard events. The seismic performance of steel liquid storage tanks is usually assessed using vulnerability curves obtained from the numerical simulation of a tank under different hazard scenarios. However, the computational demand of high-fidelity numerical simulation models, such as finite element models, makes the vulnerability assessment of liquid storage tanks time-consuming and often impractical. As a solution, this paper presents a surrogate model-based strategy for predicting seismic-induced damage in steel liquid storage tanks. In the proposed strategy, the surrogate model is leveraged to reduce the computational demand of time-consuming numerical simulations. To create the data set for training the surrogate model, field damage data from past earthquakes reconnaissance surveys and reports are collected. Features representative of steel liquid storage tank characteristics (e.g., diameter, height, liquid level, yielding stress) and seismic excitation parameters (e.g., peak ground acceleration, magnitude) are extracted from the field damage data. The collected data are then utilized to train a surrogate model that maps the relationship between tank characteristics, seismic hazard parameters, and seismic-induced damage via a data-driven surrogate model. Different types of surrogate algorithms, including naïve Bayes, k-nearest neighbors, decision tree, and random forest, are investigated, and results in terms of accuracy are reported. The model that yields the most accurate predictions is employed to predict future damage as a function of tank characteristics and seismic hazard intensity level. Results show that the proposed approach can be used to estimate the extent of damage in steel liquid storage tanks, where the use of data-driven surrogates represents a viable alternative to computationally expensive numerical simulation models.

Keywords: damage prediction , data-driven model, seismic performance, steel liquid storage tanks, surrogate model

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Authors: Aloke Bapli, Debabrata Seth

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Graphene oxide (GO) is the two-dimensional (2D) nanoscale allotrope of carbon having several physiochemical properties such as high mechanical strength, high surface area, strong thermal and electrical conductivity makes it an important candidate in various modern applications such as drug delivery, supercapacitors, sensors etc. GO has been used in the photothermal treatment of cancers and Alzheimer’s disease etc. The main idea to choose GO in our work is that it is a surface active molecule, it has a large number of hydrophilic functional groups such as carboxylic acid, hydroxyl, epoxide on its surface and in basal plane. So it can easily interact with organic fluorophores through hydrogen bonding or any other kind of interaction and easily modulate the photophysics of the probe molecules. We have used different spectroscopic techniques for our work. The Ground-state absorption spectra and steady-state fluorescence emission spectra were measured by using UV-Vis spectrophotometer from Shimadzu (model-UV-2550) and spectrofluorometer from Horiba Jobin Yvon (model-Fluoromax 4P) respectively. All the fluorescence lifetime and anisotropy decays were collected by using time-correlated single photon counting (TCSPC) setup from Edinburgh instrument (model: LifeSpec-II, U.K.). Herein, we described the photophysics of a hydrophilic molecule 7-(n,n׀-diethylamino) coumarin-3-carboxylic acid (7-DCCA) in the reverse micelles containing GO. It was observed that photophysics of dye is modulated in the presence of GO compared to photophysics of dye in the absence of GO inside the reverse micelles. Here we have reported the solvent relaxation and rotational relaxation time in GO containing reverse micelle and compare our work with normal reverse micelle system by using 7-DCCA molecule. Normal reverse micelle means reverse micelle in the absence of GO. The absorption maxima of 7-DCCA were blue shifted and emission maxima were red shifted in GO containing reverse micelle compared to normal reverse micelle. The rotational relaxation time in GO containing reverse micelle is always faster compare to normal reverse micelle. Solvent relaxation time, at lower w₀ values, is always slower in GO containing reverse micelle compare to normal reverse micelle and at higher w₀ solvent relaxation time of GO containing reverse micelle becomes almost equal to normal reverse micelle. Here emission maximum of 7-DCCA exhibit bathochromic shift in GO containing reverse micelles compared to that in normal reverse micelles because in presence of GO the polarity of the system increases, as polarity increases the emission maxima was red shifted an average decay time of GO containing reverse micelle is less than that of the normal reverse micelle. In GO containing reverse micelle quantum yield, decay time, rotational relaxation time, solvent relaxation time at λₑₓ=375 nm is always higher than λₑₓ=405 nm, shows the excitation wavelength dependent photophysics of 7-DCCA in GO containing reverse micelles.

Keywords: photophysics, reverse micelle, rotational relaxation, solvent relaxation

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Authors: M. S. Stepanova, V. V. Zakharov, P. D. Khavlyuk, I. D. Skurlov, A. Y. Dubovik, A. L. Rogach

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Carbon dots are small carbon-based spherical nanoparticles, which are typically less than 10 nm in size that can be modified with surface passivation and heteroatoms doping. The light-absorbing ability of carbon dots has attracted a significant amount of attention in photoluminescence for bioimaging and fluorescence sensing applications owing to their advantages, such as tunable fluorescence emission, photo- and thermostability and low toxicity. In this study, carbon dots were synthesized by the solvothermal method from citric acid and ethylenediamine dissolved in water. The solution was heated for 5 hours at 200°C and then cooled down to room temperature. The carbon dots films were obtained by evaporation from a high-concentration aqueous solution. The increase of both luminescence intensity and light transmission was obtained as a result of a 405 nm laser exposure to a part of the carbon dots film, which was detected using a confocal laser scanning microscope (LSM 710, Zeiss). Blueshift up to 35 nm of the luminescence spectrum is observed as luminescence intensity, which is increased more than twofold. The exact value of the shift depends on the time of the laser exposure. This shift can be caused by the modification of surface groups at the carbon dots, which are responsible for long-wavelength luminescence. In addition, a shift of the absorption peak by 10 nm and a decrease in the optical density at the wavelength of 350 nm is detected, which is responsible for the absorption of surface groups. The obtained sample was also studied with time-resolved confocal fluorescence microscope (MicroTime 100, PicoQuant), which made it possible to receive a time-resolved photoluminescence image and construct emission decays of the laser-exposed and non-exposed areas. 5 MHz pulse rate impulse laser has been used as a photoluminescence excitation source. Photoluminescence decay was approximated by two exhibitors. The laser-exposed area has the amplitude of the first-lifetime component (A1) twice as much as before, with increasing τ1. At the same time, the second-lifetime component (A2) decreases. These changes evidence a modification of the surface groups of carbon dots. The detected effect can be used to create thermostable fluorescent marks, the physical size of which is bounded by the diffraction limit of the optics (~ 200-300 nm) used for exposure and to improve the optical properties of carbon dots or in the field of optical encryption. Acknowledgements: This work was supported by the Ministry of Science and Higher Education of Russian Federation, goszadanie no. 2019-1080 and financially supported by Government of Russian Federation, Grant 08-08.

Keywords: carbon dots, photoactivation, optical properties, photoluminescence and absorption spectra

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Authors: Kimuel Suyat, Francis Aldrine Uy, John Paul Carreon

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The Philippines, composed of many islands, is connected with approximately 8030 bridges. Continuous evaluation of the structural condition of these bridges is needed to safeguard the safety of the general public. With most bridges reaching its design life, retrofitting and replacement may be needed. Concerned government agencies allocate huge costs for periodic monitoring and maintenance of these structures. The rising volume of traffic and aging of these infrastructures is challenging structural engineers to give rise for structural health monitoring techniques. Numerous techniques are already proposed and some are now being employed in other countries. Vibration Analysis is one way. The natural frequency and vibration of a bridge are design criteria in ensuring the stability, safety and economy of the structure. Its natural frequency must not be so high so as not to cause discomfort and not so low that the structure is so stiff causing it to be both costly and heavy. It is well known that the stiffer the member is, the more load it attracts. The frequency must not also match the vibration caused by the traffic loads. If this happens, a resonance occurs. Vibration that matches a systems frequency will generate excitation and when this exceeds the member’s limit, a structural failure will happen. This study presents a method for calculating dynamic fragility through the use of vibration-based monitoring system. Dynamic fragility is the probability that a structural system exceeds a limit state when subjected to dynamic loads. The bridge is modeled in SAP2000 based from the available construction drawings provided by the Department of Public Works and Highways. It was verified and adjusted based from the actual condition of the bridge. The bridge design specifications are also checked using nondestructive tests. The approach used in this method properly accounts the uncertainty of observed values and code-based structural assumptions. The vibration response of the structure due to actual loads is monitored using installed sensors on the bridge. From the determinacy of these dynamic characteristic of a system, threshold criteria can be established and fragility curves can be estimated. This study conducted in relation with the research project between Department of Science and Technology, Mapúa Institute of Technology, and the Department of Public Works and Highways also known as Mapúa-DOST Smart Bridge Project deploys Structural Health Monitoring Sensors at Zamora Bridge. The bridge is selected in coordination with the Department of Public Works and Highways. The structural plans for the bridge are also readily available.

Keywords: structural health monitoring, dynamic characteristic, threshold criteria, traffic loads

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Authors: Ayla Roberta Galaco, Juliana Fonseca De Lima, Osvaldo Antonio Serra

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Coordination polymers, also known as metal-organic frameworks (MOFs) or lanthanoide organic frameworks (LOFs) have been reported due of their promising applications in gas storage, separation, catalysis, luminescence, magnetism, drug delivery, and so on. As a type of organic–inorganic hybrid materials, the properties of coordination polymers could be chosen by deliberately selecting the organic and inorganic components. LOFs have received considerable attention because of their properties such as porosity, luminescence, and magnetism. Methods such as solvothermal synthesis are important as a strategy to control the structural and morphological properties as well as the composition of the target compounds. In this work the first solvothermal synthesis was employed to obtain the compound [Y0.4,Yb0.4,Er0.2(dmf)(for)(H2O)(tft)], by using terephthalic acid (tft) and oxalic acid, decomposed in formate (for), as ligands; Yttrium, Ytterbium and, Erbium as metal centers, in DMF and water for 4 days under 160 °C. The semi-rigid terephthalic acid (dicarboxylic) coordinates with Ln3+ ions and also is possible to form a polyfunctional bridge. On the other hand, oxalate anion has no high-energy vibrational groups, which benefits the excitation of Yb3+ in upconversion process. It was observed that the compounds with water molecules in the coordination sphere of the lanthanoide ions cause lower crystalline properties and change the structure of the LOF (1D, 2D, 3D). In the FTIR, the bands at 1589 and 1500 cm-1 correspond to the asymmetric stretching vibration of –COO. The band at 1383 cm-1 is assigned to the symmetric stretching vibration of –COO. Single crystal X-ray diffraction study reveals an infinite 3D coordination framework that crystalizes in space group P21/c. The other three products, [TR(chel)(ofd)0,5(H2O)2], where TR= Eu3+, Y3, and Yb3+/Er3+ were obtained by using 1, 2-phenylenedioxydiacetic acid (ofd) and chelidonic acid (chel) as organic ligands. Thermal analysis shows that the lanthanoide organic frameworks do not collapse at temperatures below 250 °C. By the polycrystalline X-ray diffraction patterns (PXRD) it was observed that the compounds with Eu3+, Y3+, and Yb3+/Er3+ ions are isostructural. From PXRD patterns, high crystallinity can be noticed for the complexes. The final products were characterized by single X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), energy dispersive spectroscopy (EDS) and thermogravimetric analysis (TGA). The X-ray diffraction (XRD) is an effective method to investigate crystalline properties of synthesized materials. The solid crystal obtained in the synthesis show peaks at 2θ < 10°, indicating the MOF formation. The chemical composition of LOFs was also confirmed by EDS.

Keywords: isostructural, lanthanoids, lanthanoids organic frameworks (LOFs), metal organic frameworks (MOFs), thermogravimetry, X-Ray diffraction

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Authors: Ranjita Ghoshmoulick, Aswathi Madhavan, Subhavna Juneja, Prasenjit Sen, Jaydeep Bhattacharya

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Type 2 diabetes mellitus (T2DM) is a very complex and multifactorial metabolic disease where the blood sugar level goes up. One of the major consequence of this elevated blood sugar is the formation of AGE (Advance Glycation Endproducts), from a series of chemical or biochemical reactions. AGE are detrimental because it leads to severe pathogenic complications. They are a group of structurally diverse chemical compounds formed from nonenzymatic reactions between the free amino groups (-NH2) of proteins and carbonyl groups (>C=O) of reducing sugars. The reaction is known as Maillard Reaction. It starts with the formation of reversible schiff’s base linkage which after sometime rearranges itself to form Amadori Product along with dicarbonyl compounds. Amadori products are very unstable hence rearrangement goes on until stable products are formed. During the course of the reaction a lot of chemically unknown intermediates and reactive byproducts are formed that can be termed as Early Glycation Products. And when the reaction completes, structurally stable chemical compounds are formed which is termed as Advanced Glycation Endproducts. Though all glycation products have not been characterized well, some fluorescence compounds e.g pentosidine, Malondialdehyde (MDA) or carboxymethyllysine (CML) etc as AGE and α-dicarbonyls or oxoaldehydes such as 3-deoxyglucosone (3-DG) etc as the intermediates have been identified. In this work Gold NanoParticle (GNP) was used as an optical indicator of glycation products. To achieve faster glycation kinetics and high AGE accumulation, fructose was used instead of glucose. Hemoglobin A0 (HbA0) was fructosylated by in-vitro method. AGE formation was measured fluorimetrically by recording emission at 450nm upon excitation at 350nm. Thereafter this fructosylated HbA0 was fractionated by column chromatography. Fractionation separated the proteinaceous substance from the AGEs. Presence of protein part in the fractions was confirmed by measuring the intrinsic protein fluorescence and Bradford reaction. GNPs were synthesized using the templates of chromatographically separated fractions of fructosylated HbA0. Each fractions gave rise to GNPs of varying color, indicating the presence of distinct set of glycation products differing structurally and chemically. Clear solution appeared due to settling down of particles in some vials. The reactive groups of the intermediates kept the GNP formation mechanism on and did not lead to a stable particle formation till Day 10. Whereas SPR of GNP showed monotonous colour for the fractions collected in case of non fructosylated HbA0. Our findings accentuate the use of GNPs as a simple colorimetric sensing platform for the identification of intermediates of glycation reaction which could be implicated in the prognosis of the associated health risk due to T2DM and others.

Keywords: advance glycation endproducts, glycation, gold nano particle, sensor

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Authors: Felipe M. de Freitas, Icaro V. Soares, Lucas L. L. Fortes, Sandro T. M. Gonçalves, Úrsula D. C. Resende

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The SPICE-based simulators are quite robust and widely used for simulation of electronic circuits, their algorithms support linear and non-linear lumped components and they can manipulate an expressive amount of encapsulated elements. Despite the great potential of these simulators based on SPICE in the analysis of quasi-static electromagnetic field interaction, that is, at low frequency, these simulators are limited when applied to microwave hybrid circuits in which there are both lumped and distributed elements. Usually the spatial discretization of the FDTD (Finite-Difference Time-Domain) method is done according to the actual size of the element under analysis. After spatial discretization, the Courant Stability Criterion calculates the maximum temporal discretization accepted for such spatial discretization and for the propagation velocity of the wave. This criterion guarantees the stability conditions for the leapfrogging of the Yee algorithm; however, it is known that for the field update, the stability of the complete FDTD procedure depends on factors other than just the stability of the Yee algorithm, because the FDTD program needs other algorithms in order to be useful in engineering problems. Examples of these algorithms are Absorbent Boundary Conditions (ABCs), excitation sources, subcellular techniques, grouped elements, and non-uniform or non-orthogonal meshes. In this work, the influence of the stability of the FDTD method in the modeling of concentrated elements such as resistive sources, resistors, capacitors, inductors and diode will be evaluated. In this paper is proposed, therefore, the electromagnetic modeling of electronic components in order to create models that satisfy the needs for simulations of circuits in ultra-wide frequencies. The models of the resistive source, the resistor, the capacitor, the inductor, and the diode will be evaluated, among the mathematical models for lumped components in the LE-FDTD method (Lumped-Element Finite-Difference Time-Domain), through the parametric analysis of Yee cells size which discretizes the lumped components. In this way, it is sought to find an ideal cell size so that the analysis in FDTD environment is in greater agreement with the expected circuit behavior, maintaining the stability conditions of this method. Based on the mathematical models and the theoretical basis of the required extensions of the FDTD method, the computational implementation of the models in Matlab® environment is carried out. The boundary condition Mur is used as the absorbing boundary of the FDTD method. The validation of the model is done through the comparison between the obtained results by the FDTD method through the electric field values and the currents in the components, and the analytical results using circuit parameters.

Keywords: hybrid circuits, LE-FDTD, lumped element, parametric analysis

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Authors: S. V. Kuznetsov, M. N. Mayakova, V. Yu. Proydakova, V. V. Pavlov, A. S. Nizamutdinov, O. A. Morozov, V. V. Voronov, P. P. Fedorov

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Increase in the share of electricity received by conversion of solar energy results in the reduction of the industrial impact on the environment from the use of the hydrocarbon energy sources. One way to increase said share is to improve the efficiency of solar energy conversion in silicon-based solar panels. Such efficiency increase can be achieved by transferring energy from sunlight-insensitive areas of work of silicon solar panels to the area of their photoresistivity. To achieve this goal, a transition to new luminescent materials with the high quantum yield of luminescence is necessary. Improvement in the quantum yield can be achieved by quantum cutting, which allows obtaining a quantum yield of down conversion of more than 150% due to the splitting of high-energy photons of the UV spectral range into lower-energy photons of the visible and near infrared spectral ranges. The goal of present work is to test approach of excitation through sensibilization of 4f-4f fluorescence of Yb3+ by various RE ions absorbing in UV and Vis spectral ranges. One of promising materials for quantum cutting luminophores are fluorides. In our investigation we have developed synthesis of nano- and submicron powders of calcium fluoride and strontium doped with rare-earth elements (Yb: Ce, Yb: Pr, Yb: Eu) of controlled dimensions and shape by co-precipitation from water solution technique. We have used Ca(NO3)2*4H2O, Sr(NO3)2, HF, NH4F as precursors. After initial solutions of nitrates were prepared they have been mixed with fluorine containing solution by dropwise manner. According to XRD data, the synthesis resulted in single phase samples with fluorite structure. By means of SEM measurements, we have confirmed spherical morphology and have determined sizes of particles (50-100 nm after synthesis and 150-300 nm after calcination). Temperature of calcination appeared to be 600°C. We have investigated the spectral-kinetic characteristics of above mentioned compounds. Here the diffuse reflection and laser induced fluorescence spectra of Yb3+ ions excited at around 4f-4f and 4f-5d transitions of Pr3+, Eu3+ and Ce3+ ions in the synthesized powders are reported. The investigation of down conversion luminescence capability of synthesized compounds included measurements of fluorescence decays and quantum yield of 2F5/2-2F7/2 fluorescence of Yb3+ ions as function of Yb3+ and sensitizer contents. An optimal chemical composition of CaF2-YbF3- LnF3 (Ln=Ce, Eu, Pr), SrF2-YbF3-LnF3 (Ln=Ce, Eu, Pr) micro- and nano- powders according to criteria of maximal IR fluorescence yield is proposed. We suppose that investigated materials are prospective in solar panels improvement applications. Work was supported by Russian Science Foundation grant #17-73- 20352.

Keywords: solar cell, fluorides, down-conversion luminescence, maximum quantum yield

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Authors: Ali H. Daraji, Jack M. Hale, Ye Jianqiao

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With the extensive use of high specific strength structures to optimise the loading capacity and material cost in aerospace and most engineering applications, much effort has been expended to develop intelligent structures for active vibration reduction and structural health monitoring. These structures are highly flexible, inherently low internal damping and associated with large vibration and long decay time. The modification of such structures by adding lightweight piezoelectric sensors and actuators at efficient locations integrated with an optimal control scheme is considered an effective solution for structural vibration monitoring and controlling. The size and location of sensor and actuator are important research topics to investigate their effects on the level of vibration detection and reduction and the amount of energy provided by a controller. Several methodologies have been presented to determine the optimal location of a limited number of sensors and actuators for small-scale structures. However, these studies have tackled this problem directly, measuring the fitness function based on eigenvalues and eigenvectors achieved with numerous combinations of sensor/actuator pair locations and converging on an optimal set using heuristic optimisation techniques such as the genetic algorithms. This is computationally expensive for small- and large-scale structures subject to optimise a number of s/a pairs to suppress multiple vibration modes. This paper proposes an efficient method to determine optimal locations for a limited number of sensor/actuator pairs for active vibration reduction of a flexible structure based on finite element method and Hamilton’s principle. The current work takes the simplified approach of modelling a structure with sensors at all locations, subjecting it to an external force to excite the various modes of interest and noting the locations of sensors giving the largest average percentage sensors effectiveness measured by dividing all sensor output voltage over the maximum for each mode. The methodology was implemented for a cantilever plate under external force excitation to find the optimal distribution of six sensor/actuator pairs to suppress the first six modes of vibration. It is shown that the results of the optimal sensor locations give good agreement with published optimal locations, but with very much reduced computational effort and higher effectiveness. Furthermore, it is shown that collocated sensor/actuator pairs placed in these locations give very effective active vibration reduction using optimal linear quadratic control scheme.

Keywords: optimisation, plate, sensor effectiveness, vibration control

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Authors: Oubelkacem Yacine, El Bast Hassan, El Bakkali Abdelmajid, Lamhasni Taibi, Ettakni Mahmoud, Ait Lyazidi Saadia, Haddad Mustapha, Ben-Ncer Abdelouahed, El Ferrane Mohammed, Boufarra Abdelkrim

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The present work relates to an on-site and completely non-invasive investigation of one of the most famous west Mediterranean Torah Scroll housed at the National Library of the Kingdom of Morocco. The scroll is 26 m long and consists of 143 parchment sheets of 59 cm x 19 cm, exhibiting only black writings; it is of unknown age. The artifact has been restored by the curator staff of the library. The investigation exploring separately the parchment support and the writing black ink aims at: i) the examination of the parchment conservation/degradation state, ii) the identification of the black ink and iii) the identification of the parchment handcrafting materials. For this purpose, the analyses have been based on combining all of elemental XRF and structural Raman, ATR-FT Infrared Red and Fiber Optical Reflectance spectroscopies, in addition to chroma-metric and pH measurements. pH measurements showing values around 6.5 are in concordance with the absence of any visual corrosion related to the parchment acidity. However, on the basis of the relative intensities and frequency shift of amid I (AI) and amid II (AII) vibrational bands of the collagen, ATR-FTIR spectra revealed diffuse hydrolysis and gelatinization of the parchment writing support; diffuse and non-homogeny degradation by gelatinization has been also confirmed by the IG gelatinization index deduced from the NIR bands on the FOR spectra. This IG index, defined as the ratio I (6860 cm-1) / I (6685 cm-1), ranges in the interval 0.98 – 1 and highlights collagen degradation at the molecular level. Sequentially Shifted Excitation Raman measurements (SSERS) crossed to X-ray fluorescence (XRF) ones on the black writings revealed that the black ink used is an iron-copper gall one, while FOR spectra are typical of pure metal gall inks. These later reflectance measurements exclude, thus, any intentional addition of carbon black to the ink recipe. Moreover, no lead white had been used while pre-drawing the writing lines. On another side, ATR-FTIR measurements highlighted the presence of oxalates as ink degradation products. Considering the parchment handcrafting, the combination of XRF and ATR-FTIR measurements led to the assumption that this writing support had been prepared according to ancient Middle East practices; the parchment infrared fingerprint seems identical to that of the Dead Sea scroll. The present multi-technical analyses are the first ones performed on an ancient Judaic written parchment of Morocco; it is under furthering. The investigation will be extended to other parchments belonging to the Jewish Cultural Heritage Museum of Morocco in Casablanca.

Keywords: torah scroll, parchment, black ink, non-invasive analyses, XRF/ATR-FTIR/RAMAN/FORS

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Authors: Sankha Chakrabortty, Biswajit Ruj, Parimal Pal

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Methanol is one of the most important chemical products and intermediates. It can be used as a solvent, intermediate or raw material for a number of higher valued products, fuels or additives. From the last one decay, the total global demand of methanol has increased drastically which forces the scientists to produce a large amount of methanol from a renewable source to meet the global demand with a sustainable way. Different types of non-renewable based raw materials have been used for the synthesis of methanol on a large scale which makes the process unsustainable. In this circumstances, photocatalytic conversion of CO₂ into methanol under solar/UV excitation becomes a viable approach to give a sustainable production approach which not only meets the environmental crisis by recycling CO₂ to fuels but also reduces CO₂ amount from the atmosphere. Development of such sustainable production approach for CO₂ conversion into methanol still remains a major challenge in the current research comparing with conventional energy expensive processes. In this backdrop, the development of environmentally friendly materials, like photocatalyst has taken a great perspective for methanol synthesis. Scientists in this field are always concerned about finding an improved photocatalyst to enhance the photocatalytic performance. Graphene-based hybrid and composite materials with improved properties could be a better nanomaterial for the selective conversion of CO₂ to methanol under visible light (solar energy) or UV light. The present invention relates to synthesis an improved heterogeneous graphene-based photocatalyst with improved catalytic activity and surface area. Graphene with enhanced surface area is used as coupled material of copper-loaded titanium oxide to improve the electron capture and transport properties which substantially increase the photoinduced charge transfer and extend the lifetime of photogenerated charge carriers. A fast reduction method through H₂ purging has been adopted to synthesis improved graphene whereas ultrasonication based sol-gel method has been applied for the preparation of graphene coupled copper loaded titanium oxide with some enhanced properties. Prepared photocatalysts were exhaustively characterized using different characterization techniques. Effects of catalyst dose, CO₂ flow rate, reaction temperature and stirring time on the efficacy of the system in terms of methanol yield and productivity have been studied in the present study. The study shown that the newly synthesized photocatalyst with an enhanced surface resulting in a sustained productivity and yield of methanol 0.14 g/Lh, and 0.04 g/gcat respectively, after 3 h of illumination under UV (250W) at an optimum catalyst dosage of 10 g/L having 1:2:3 (Graphene: TiO₂: Cu) weight ratio.

Keywords: renewable energy, CO₂ capture, photocatalytic conversion, methanol

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Authors: Bastian Waduge Naveen Harindu Hemasiri, Jae-Kwan Kim, Ji-Myon Lee

Abstract:

Indium tin oxide (ITO) remains the industrial standard transparent conducting oxides with better performances. Recently, graphene becomes as a strong material with unique properties to replace the ITO. However, graphene/ITO hybrid composite material is a newly born field in the electronic world. In this study, the graphene/ITO composite bi-film was synthesized by a two steps process. 10 wt.% tin-doped, ITO thin films were produced by an environmentally friendly aqueous sol-gel spin coating technique with economical salts of In(NO3)3.H2O and SnCl4 without using organic additives. The wettability and surface free energy (97.6986 mJ/m2) enhanced oxygen plasma treated glass substrates were used to form voids free continuous ITO film. The spin-coated samples were annealed at 600 0C for 1 hour under low vacuum conditions to obtained crystallized, ITO film. The crystal structure and crystalline phases of ITO thin films were analyzed by X-ray diffraction (XRD) technique. The Scherrer equation was used to determine the crystallite size. Detailed information about chemical composition and elemental composition of the ITO film were determined by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) coupled with FE-SEM respectively. Graphene synthesis was done under chemical vapor deposition (CVD) method by using Cu foil at 1000 0C for 1 min. The quality of the synthesized graphene was characterized by Raman spectroscopy (532nm excitation laser beam) and data was collected at room temperature and normal atmosphere. The surface and cross-sectional observation were done by using FE-SEM. The optical transmission and sheet resistance were measured by UV-Vis spectroscopy and four point probe head at room temperature respectively. Electrical properties were also measured by using V-I characteristics. XRD patterns reveal that the films contain the In2O3 phase only and exhibit the polycrystalline nature of the cubic structure with the main peak of (222) plane. The peak positions of In3d5/2 (444.28 eV) and Sn3d5/2 (486.7 eV) in XPS results indicated that indium and tin are in the oxide form only. The UV-visible transmittance shows 91.35 % at 550 nm with 5.88 x 10-3 Ωcm specific resistance. The G and 2D band in Raman spectroscopy of graphene appear at 1582.52 cm-1 and 2690.54 cm-1 respectively when the synthesized CVD graphene on SiO2/Si. The determined intensity ratios of 2D to G (I2D/IG) and D to G (ID/IG) were 1.531 and 0.108 respectively. However, the above-mentioned G and 2D peaks appear at 1573.57 cm-1 and 2668.14 cm-1 respectively when the CVD graphene on the ITO coated glass, the positions of G and 2D peaks were red shifted by 8.948 cm-1 and 22.396 cm-1 respectively. This graphene/ITO bi-film shows modified electrical properties when compares with sol-gel derived ITO film. The reduction of sheet resistance in the bi-film was 12.03 % from the ITO film. Further, the fabricated graphene/ITO bi-film shows 88.66 % transmittance at 550 nm wavelength.

Keywords: chemical vapor deposition, graphene, ITO, Raman Spectroscopy, sol-gel

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Authors: Vipin Kumar, Girish S. Setlur

Abstract:

Graphene has been recognized as a promising 2D material with many new properties. However, pristine graphene is gapless which hinders its direct application towards graphene-based semiconducting devices. Graphene is a zero-gapp and linearly dispersing semiconductor. Massless charge carriers (quasi-particles) in graphene obey the relativistic Dirac equation. These Dirac fermions show very unusual physical properties such as electronic, optical and transport. Graphene is analogous to two-level atomic systems and conventional semiconductors. We may expect that graphene-based systems will also exhibit phenomena that are well-known in two-level atomic systems and in conventional semiconductors. Rabi oscillation is a nonlinear optical phenomenon well-known in the context of two-level atomic systems and also in conventional semiconductors. It is the periodic exchange of energy between the system of interest and the electromagnetic field. The present work describes the phenomenon of Rabi oscillations in graphene based systems. Rabi oscillations have already been described theoretically and experimentally in the extensive literature available on this topic. To describe Rabi oscillations they use an approximation known as rotating wave approximation (RWA) well-known in studies of two-level systems. RWA is valid only near conventional resonance (small detuning)- when the frequency of the external field is nearly equal to the particle-hole excitation frequency. The Rabi frequency goes through a minimum close to conventional resonance as a function of detuning. Far from conventional resonance, the RWA becomes rather less useful and we need some other technique to describe the phenomenon of Rabi oscillation. In conventional systems, there is no second minimum - the only minimum is at conventional resonance. But in graphene we find anomalous Rabi oscillations far from conventional resonance where the Rabi frequency goes through a minimum that is much smaller than the conventional Rabi frequency. This is known as anomalous Rabi frequency and is unique to graphene systems. We have shown that this is attributable to the pseudo-spin degree of freedom in graphene systems. A new technique, which is an alternative to RWA called asymptotic RWA (ARWA), has been invoked by our group to discuss the phenomenon of Rabi oscillation. Experimentally accessible current density shows different types of threshold behaviour in frequency domain close to the anomalous Rabi frequency depending on the system chosen. For single layer graphene, the exponent at threshold is equal to 1/2 while in case of bilayer graphene, it is computed to be equal to 1. Bilayer graphene shows harmonic (anomalous) resonances absent in single layer graphene. The effect of asymmetry and trigonal warping (a weak direct inter-layer hopping in bilayer graphene) on these oscillations is also studied in graphene systems. Asymmetry has a remarkable effect only on anomalous Rabi oscillations whereas the Rabi frequency near conventional resonance is not significantly affected by the asymmetry parameter. In presence of asymmetry, these graphene systems show Rabi-like oscillations (offset oscillations) even for vanishingly small applied field strengths (less than the gap parameter). The frequency of offset oscillations may be identified with the asymmetry parameter.

Keywords: graphene, Bilayer graphene, Rabi oscillations, Dirac fermion systems

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Authors: Anna V. Zaporozhchenko, Dmytro Kutnyakhov, Katherina Medjanik, Christian Tusche, Hans-Joachim Elmers, Olena Fedchenko, Sergey Chernov, Martin Ellguth, Sergej A. Nepijko, Gerd Schoenhense

Abstract:

Graphene reveals a unique electronic structure that predetermines many intriguing properties such as massless charge carriers, optical transparency and high velocity of fermions at the Fermi level, opening a wide horizon of future applications. Hence, a detailed investigation of the electronic structure of graphene is crucial. The method of choice is angular resolved photoelectron spectroscopy ARPES. Here we present experiments using time-of-flight (ToF) momentum microscopy, being an alternative way of ARPES using full-field imaging of the whole Brillouin zone (BZ) and simultaneous acquisition of up to several 100 energy slices. Unlike conventional ARPES, k-microscopy is not limited in simultaneous k-space access. We have recorded the whole first BZ of graphene on Ir(111) including all six Dirac cones. As excitation source we used synchrotron radiation from BESSY II (Berlin) at the U125-2 NIM, providing linearly polarized (both polarizations p- and s-) VUV radiation. The instrument uses a delay-line detector for single-particle detection up the 5 Mcps range and parallel energy detection via ToF recording. In this way, we gather a 3D data stack I(E,kx,ky) of the full valence electronic structure in approx. 20 mins. Band dispersion stacks were measured in the energy range of 14 eV up to 23 eV with steps of 1 eV. The linearly-dispersing graphene bands for all six K and K’ points were simultaneously recorded. We find clear features of hybridization with the substrate, in particular in the linear dichroism in the angular distribution (LDAD). Recording of the whole Brillouin zone of graphene/Ir(111) revealed new features. First, the intensity differences (i.e. the LDAD) are very sensitive to the interaction of graphene bands with substrate bands. Second, the dark corridors are investigated in detail for both, p- and s- polarized radiation. They appear as local distortions of photoelectron current distribution and are induced by quantum mechanical interference of graphene sublattices. The dark corridors are located in different areas of the 6 Dirac cones and show chirality behaviour with a mirror plane along vertical axis. Moreover, two out of six show an oval shape while the rest are more circular. It clearly indicates orientation dependence with respect to E vector of incident light. Third, a pattern of faint but very sharp lines is visible at energies around 22eV that strongly remind on Kikuchi lines in diffraction. In conclusion, the simultaneous study of all six Dirac cones is crucial for a complete understanding of dichroism phenomena and the dark corridor.

Keywords: band structure, graphene, momentum microscopy, LDAD

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Authors: Riya Bose, Ashok Bera, Manas R. Parida, Anirudhha Adhikari, Basamat S. Shaheen, Erkki Alarousu, Jingya Sun, Tom Wu, Osman M. Bakr, Omar F. Mohammed

Abstract:

This work reports visualization of charge carrier dynamics on the surface of copper indium gallium selenide (CIGSe) nanocrystals in real space and time using four-dimensional scanning ultrafast electron microscopy (4D S-UEM) and correlates it with the optoelectronic properties of the nanocrystals. The surface of the nanocrystals plays a key role in controlling their applicability for light emitting and light harvesting purposes. Typically for quaternary systems like CIGSe, which have many desirable attributes to be used for optoelectronic applications, relative abundance of surface trap states acting as non-radiative recombination centre for charge carriers remains as a major bottleneck preventing further advancements and commercial exploitation of these nanocrystals devices. Though ultrafast spectroscopic techniques allow determining the presence of picosecond carrier trapping channels, because of relative larger penetration depth of the laser beam, only information mainly from the bulk of the nanocrystals is obtained. Selective mapping of such ultrafast dynamical processes on the surfaces of nanocrystals remains as a key challenge, so far out of reach of purely optical probing time-resolved laser techniques. In S-UEM, the optical pulse generated from a femtosecond (fs) laser system is used to generate electron packets from the tip of the scanning electron microscope, instead of the continuous electron beam used in the conventional setup. This pulse is synchronized with another optical excitation pulse that initiates carrier dynamics in the sample. The principle of S-UEM is to detect the secondary electrons (SEs) generated in the sample, which is emitted from the first few nanometers of the top surface. Constructed at different time delays between the optical and electron pulses, these SE images give direct and precise information about the carrier dynamics on the surface of the material of interest. In this work, we report selective mapping of surface dynamics in real space and time of CIGSe nanocrystals applying 4D S-UEM. We show that the trap states can be considerably passivated by ZnS shelling of the nanocrystals, and the carrier dynamics can be significantly slowed down. We also compared and discussed the S-UEM kinetics with the carrier dynamics obtained from conventional ultrafast time-resolved techniques. Additionally, a direct effect of the state trap removal can be observed in the enhanced photoresponse of the nanocrystals after shelling. Direct observation of surface dynamics will not only provide a profound understanding of the photo-physical mechanisms on nanocrystals’ surfaces but also enable to unlock their full potential for light emitting and harvesting applications.

Keywords: 4D scanning ultrafast microscopy, charge carrier dynamics, nanocrystals, optoelectronics, surface passivation, trap states

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Authors: E. Nakamachi, S. Tanaka, K. Yamamoto, Y. Morita

Abstract:

In this study, we developed a three-dimensional (3D) direct current electric field (DCEF) stimulation bio-reactor for axonal outgrowth enhancement to generate the neural network of the central nervous system (CNS). By using our newly developed 3D DCEF stimulation bio-reactor, we cultured the rat pheochromocytoma cells (PC12) and investigated the effects on the axonal extension enhancement and network generation. Firstly, we designed and fabricated a 3D bio-reactor, which can load DCEF stimulation on PC12 cells embedded in the collagen gel as extracellular environment. The connection between the electrolyte and the medium using salt bridges for DCEF stimulation was introduced to avoid the cell death by the toxicity of metal ion. The distance between the salt bridges was adopted as the design variable to optimize a structure for uniform DCEF stimulation, where the finite element (FE) analyses results were used. Uniform DCEF strength and electric flux vector direction in the PC12 cells embedded in collagen gel were examined through measurements of the fabricated 3D bio-reactor chamber. Measurement results of DCEF strength in the bio-reactor showed a good agreement with FE results. In addition, the perfusion system was attached to maintain pH 7.2 ~ 7.6 of the medium because pH change was caused by DCEF stimulation loading. Secondly, we disseminated PC12 cells in collagen gel and carried out 3D culture. Finally, we measured the morphology of PC12 cell bodies and neurites by the multiphoton excitation fluorescence microscope (MPM). The effectiveness of DCEF stimulation to enhance the axonal outgrowth and the neural network generation was investigated. We confirmed that both an increase of mean axonal length and axogenesis rate of PC12, which have been exposed 5 mV/mm for 6 hours a day for 4 days in the bioreactor. We found following conclusions in our study. 1) Design and fabrication of DCEF stimulation bio-reactor capable of 3D culture nerve cell were completed. A uniform electric field strength of average value of 17 mV/mm within the 1.2% error range was confirmed by using FE analyses, after the structure determination through the optimization process. In addition, we attached a perfusion system capable of suppressing the pH change of the culture solution due to DCEF stimulation loading. 2) Evaluation of DCEF stimulation effects on PC12 cell activity was executed. The 3D culture of PC 12 was carried out adopting the embedding culture method using collagen gel as a scaffold for four days under the condition of 5.0 mV/mm and 10mV/mm. There was a significant effect on the enhancement of axonal extension, as 11.3% increase in an average length, and the increase of axogenesis rate. On the other hand, no effects on the orientation of axon against the DCEF flux direction was observed. Further, the network generation was enhanced to connect longer distance between the target neighbor cells by DCEF stimulation.

Keywords: PC12, DCEF stimulation, 3D bio-reactor, axonal extension, neural network generation

Procedia PDF Downloads 184

Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

Abstract:

Photoinduced tautomerization reactions have been the centre of attention among the scientific community over the past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried out on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phases. Derivatives of the above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are studies in the solution phase that suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization-time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy, i.e., fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to the S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1, whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red-shifted transition in the case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV which is significantly higher than the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in the case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red-shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronically excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in the excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: excited state hydrogen transfer, supersonic expansion, gas phase spectroscopy, IR-UV double resonance spectroscopy, laser induced fluorescence, photoionization efficiency spectroscopy

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Authors: Zélia Maria Da Costa Ludwig, Maria José Valenzuela Bell, Geraldo Henriques Da Silva, Thales Alves Faraco, Victor Rocha Da Silva, Daniel Rotmeister Teixeira, Vírgilio De Carvalho Dos Anjos, Valdemir Ludwig

Abstract:

Advances in telecommunications grow with the development of optical amplifiers based on rare earth ions. The focus has been concentrated in silicate glasses although their amplified spontaneous emission is limited to a few tens of nanometers (~ 40nm). Recently, phosphate glasses have received great attention due to their potential application in optical data transmission, detection, sensors and laser detector, waveguide and optical fibers, besides its excellent physical properties such as high thermal expansion coefficients and low melting temperature. Compared with the silica glasses, phosphate glasses provide different optical properties such as, large transmission window of infrared, and good density. Research on the improvement of physical and chemical durability of phosphate glass by addition of heavy metals oxides in P2O5 has been performed. The addition of Na2O further improves the solubility of rare earths, while increasing the Al2O3 links in the P2O5 tetrahedral results in increased durability and aqueous transition temperature and a decrease of the coefficient of thermal expansion. This work describes the structural and spectroscopic characterization of a phosphate glass matrix doped with different Er (Erbium) concentrations. The phosphate glasses containing Er3+ ions have been prepared by melt technique. A study of the optical absorption, luminescence and lifetime was conducted in order to characterize the infrared emission of Er3+ ions at 1540 nm, due to the radiative transition 4I13/2 → 4I15/2. Our results indicate that the present glass is a quite good matrix for Er3+ ions, and the quantum efficiency of the 1540 nm emission was high. A quenching mechanism for the mentioned luminescence was not observed up to 2,0 mol% of Er concentration. The Judd-Ofelt parameters, radiative lifetime and quantum efficiency have been determined in order to evaluate the potential of Er3+ ions in new phosphate glass. The parameters follow the trend as Ω2 > Ω4 > Ω6. It is well known that the parameter Ω2 is an indication of the dominant covalent nature and/or structural changes in the vicinity of the ion (short range effects), while Ω4 and Ω6 intensity parameters are long range parameters that can be related to the bulk properties such as viscosity and rigidity of the glass. From the PL measurements, no red or green upconversion was measured when pumping the samples with laser excitation at 980 nm. As future prospects: Synthesize this glass system with silver in order to determine the influence of silver nanoparticles on the Er3+ ions.

Keywords: phosphate glass, erbium, luminescence, glass system

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Authors: Adinew Gebremeskel Tizazu

Abstract:

The effect of soil-structure interaction on the dynamic response of reinforced concrete buildings of regular and symmetrical geometry are considered in this study. The structures are presumed to be generally embedded in a homogenous soil formation underlain by very stiff material or bedrock. The structure-foundation–soil system is excited at the base by an earthquake ground motion. The superstructure is idealized as a system with lumped masses concentrated at the floor levels, and coupled with the substructure. The substructure system, which comprises of the foundation and soil, is represented, and replaced by springs and dashpots. Frequency-dependent impedances of the foundation system are incorporated in the discrete model in terms of the springs and dashpots coefficients. The excitation applied to the model is field ground motions of actual earthquake records. Modal superposition principle is employed to transform the equations of motion in geometrical coordinates to modal coordinates. However, the modal equations remain coupled with respect to damping terms due to the difference in damping mechanisms of the superstructure and the soil. Hence, proportional damping for the coupled structural system may not be assumed. An iterative approach is adopted and programmed to solve the system of coupled equations of motion in modal coordinates to obtain the displacement responses of the system. Parametric studies for responses of building structures with regular and symmetric plans of different structural properties and heights are made for fixed and flexible base conditions, for different soil conditions encountered in Addis Ababa. The displacement, base shear and base overturning moments are used in the comparison of different types of structures for various foundation embedment depths, site conditions and height of structures. These values are compared against those of fixed base structure. The study shows that the flexible base structures, generally exhibit different responses from those structures with fixed base. Basically, the natural circular frequencies, the base shears and the inter-story displacements for the flexible base are less than those of the fixed base structures. This trend is particularly evident when the flexible soil has large thickness. In contrast, the trend becomes less predictable, when the thickness of the flexible soil decreases. Moreover, in the latter case, the iteration undulates significantly making the prediction difficult. This is attributed to the highly jagged nature of the impedance functions of frequencies for such formations. In this case, it is difficult to conclude whether the conventional fixed-base approach yields conservative design forces, as is the case for soil formations of large thickness.

Keywords: effect of soil structure, dynamic response corroborated, the modal superposition principle, parametric studies

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Authors: Takeru Furuawa, Kohei Takizawa, Daisuke Kuwahara, Shunjiro Shinohara

Abstract:

In the field of a space propulsion, an electric propulsion system has been developed because its fuel efficiency is much higher than a conventional chemical one. However, the practical electric propulsion systems, e.g., an ion engine, have a problem of short lifetime due to a damage of generation and acceleration electrodes of the plasma. A helicon plasma thruster is proposed as a long-lifetime electric thruster which has non-direct contact electrodes. In this system, both generation and acceleration methods of a dense plasma are executed by antennas from the outside of a discharge tube. Development of the helicon plasma thruster has been conducting under the Helicon Electrodeless Advanced Thruster (HEAT) project. Our helicon plasma thruster has two important processes. First, we generate a dense source plasma using a helicon wave with an excitation frequency between an ion and an electron cyclotron frequencies, fci and fce, respectively, applied from the outside of a discharge using a radio frequency (RF) antenna. The helicon plasma source can provide a high-density (~1019 m-3), a high-ionization ratio (up to several tens of percent), and a high particle generation efficiency. Second, in order to achieve high thrust and specific impulse, we accelerate the dense plasma by the axial Lorentz force fz using the product of the induced azimuthal current jθ and the static radial magnetic field Br, shown as fz = jθ × Br. The HEAT project has proposed several kinds of electrodeless acceleration schemes, and in our particular case, a Rotating Magnetic Field (RMF) method has been extensively studied. The RMF scheme was originally developed as a concept to maintain the Field Reversed Configuration (FRC) in a magnetically confined fusion research. Here, RMF coils are expected to generate jθ due to a nonlinear effect shown below. First, the rotating magnetic field Bω is generated by two pairs of RMF coils with AC currents, which have a phase difference of 90 degrees between the pairs. Due to the Faraday’s law, an axial electric field is induced. Second, an axial current is generated by the effects of an electron-ion and an electron-neutral collisions through the Ohm’s law. Third, the azimuthal electric field is generated by the nonlinear term, and the retarding torque generated by the collision effects again. Then, azimuthal current jθ is generated as jθ = - nₑ er ∙ 2π fRMF. Finally, the axial Lorentz force fz for plasma acceleration is generated. Here, jθ is proportional to nₑ and frequency of RMF coil current fRMF, when Bω is fully penetrated into the plasma. Our previous study has achieved 19 % increase of ion velocity using the 5 MHz and 50 A of the RMF coil power supply. In this presentation, we will show the improvement of the ion velocity using the lower frequency and higher current supplied by RMF power supply. In conclusion, helicon high-density plasma production and electromagnetic acceleration by the RMF scheme with a concept of electrodeless condition have been successfully executed.

Keywords: electric propulsion, electrodeless thruster, helicon plasma, rotating magnetic field

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Authors: Simona Dostalova, Pavel Kopel, Marketa Vaculovicova, Vojtech Adam, Rene Kizek

Abstract:

Protein apoferritin seems to be a very promising structure for use as a nanocarrier. It is prepared from intracellular ferritin protein naturally found in most organisms. The role of ferritin proteins is to store and transport ferrous ions. Apoferritin is a hollow protein cage without ferrous ions that can be prepared from ferritin by reduction with thioglycolic acid or dithionite. The structure of apoferritin is composed of 24 protein subunits, creating a sphere with 12 nm in diameter. The inner cavity has a diameter of 8 nm. The drug encapsulation process is based on the response of apoferritin structure to the pH changes of surrounding solution. In low pH, apoferritin is disassembled into individual subunits and its structure is “opened”. It can then be mixed with any desired cytotoxic drug and after adjustment of pH back to neutral the subunits are reconnected again and the drug is encapsulated within the apoferritin particles. Excess drug molecules can be removed by dialysis. The receptors for apoferritin, SCARA5 and TfR1 can be found in the membrane of both healthy and cancer cells. To enhance the specific targeting of apoferritin nanocarrier, it is possible to modify its surface with targeting moieties, such as antibodies. To ensure sterically correct complex, we used a a peptide linker based on a protein G with N-terminus affinity towards Fc region of antibodies. To connect the peptide to the surface of apoferritin, the C-terminus of peptide was made of cysteine with affinity to gold. The surface of apoferritin with encapsulated doxorubicin (ApoDox) was coated either with gold nanoparticles (ApoDox-Nano) or gold (III) chloride hydrate reduced with sodium borohydride (ApoDox-HAu). The applied amount of gold in form of gold (III) chloride hydrate was 10 times higher than in the case of gold nanoparticles. However, after removal of the excess unbound ions by electrophoretic separation, the concentration of gold on the surface of apoferritin was only 6 times higher for ApoDox-HAu in comparison with ApoDox-Nano. Moreover, the reduction with sodium borohydride caused a loss of doxorubicin fluorescent properties (excitation maximum at 480 nm with emission maximum at 600 nm) and thus its biological activity. Fluorescent properties of ApoDox-Nano were similar to the unmodified ApoDox, therefore it was more suited for the intended use. To evaluate the specificity of apoferritin modified with antibodies, we used ELISA-like method with the surface of microtitration plate wells coated by the antigen (goat anti-human IgG antibodies). To these wells, we applied ApoDox without targeting antibodies and ApoDox-Nano modified with targeting antibodies (human IgG antibodies). The amount of unmodified ApoDox on antigen after incubation and subsequent rinsing with water was 5 times lower than in the case of ApoDox-Nano modified with targeting antibodies. The modification of non-gold ApoDox with antibodies caused no change in its targeting properties. It can therefore be concluded that the demonstrated procedure allows us to create nanocarrier with enhanced targeting properties, suitable for nanomedicine.

Keywords: apoferritin, doxorubicin, nanocarrier, targeting antibodies

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Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

Abstract:

Photoinduced tautomerization reactions have been the centre of attention among scientific community over past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered as a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phase. Derivatives of above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are a few studies in the solution phase which suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy i.e. fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1 whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red shifted transition in case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV, which is significantly higher that the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronic excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: photoinduced tautomerization reactions, gas phse spectroscopy, ), IR-UV double resonance spectroscopy, resonant two-photon ionization time of flight mass spectrometry (2C-R2PI)

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Authors: Xiaoyong He

Abstract:

The manipulation of THz waves is still a challenging task due to lack of natural materials interacted with it strongly. Designed by tailoring the characters of unit cells (meta-molecules), the advance of metamaterials (MMs) may solve this problem. However, because of Ohmic and radiation losses, the performance of MMs devices is subjected to the dissipation and low quality factor (Q-factor). This dilemma may be circumvented by Fano resonance, which arises from the destructive interference between a bright continuum mode and dark discrete mode (or a narrow resonance). Different from symmetric Lorentz spectral curve, Fano resonance indicates a distinct asymmetric line-shape, ultrahigh quality factor, steep variations in spectrum curves. Fano resonance is usually realized through symmetry breaking. However, if concentric double rings (DR) are placed closely to each other, the near-field coupling between them gives rise to two hybridized modes (bright and narrowband dark modes) because of the local asymmetry, resulting into the characteristic Fano line shape. Furthermore, from the practical viewpoint, it is highly desirable requirement that to achieve the modulation of Fano spectral curves conveniently, which is an important and interesting research topics. For current Fano systems, the tunable spectral curves can be realized by adjusting the geometrical structural parameters or magnetic fields biased the ferrite-based structure. But due to limited dispersion properties of active materials, it is still a tough work to tailor Fano resonance conveniently with the fixed structural parameters. With the favorable properties of extreme confinement and high tunability, graphene is a strong candidate to achieve this goal. The DR-structure possesses the excitation of so-called “trapped modes,” with the merits of simple structure and high quality of resonances in thin structures. By depositing graphene circular DR on the SiO2/Si/ polymer substrate, the tunable Fano resonance has been theoretically investigated in the terahertz regime, including the effects of graphene Fermi level, structural parameters and operation frequency. The results manifest that the obvious Fano peak can be efficiently modulated because of the strong coupling between incident waves and graphene ribbons. As Fermi level increases, the peak amplitude of Fano curve increases, and the resonant peak position shifts to high frequency. The amplitude modulation depth of Fano curves is about 30% if Fermi level changes in the scope of 0.1-1.0 eV. The optimum gap distance between DR is about 8-12 μm, where the value of figure of merit shows a peak. As the graphene ribbon width increases, the Fano spectral curves become broad, and the resonant peak denotes blue shift. The results are very helpful to develop novel graphene plasmonic devices, e.g. sensors and modulators.

Keywords: graphene, metamaterials, terahertz, tunable

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Authors: Ming-Hsiang Shih, Wen-Pei Sung, Shih-Heng Tung

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The purposes of hydraulic gate are to maintain the functions of storing and draining water. It bears long-term hydraulic pressure and earthquake force and is very important for reservoir and waterpower plant. The high tensile strength of steel plate is used as constructional material of hydraulic gate. The cracks and rusts, induced by the defects of material, bad construction and seismic excitation and under water respectively, thus, the mechanics phenomena of gate with crack are probing into the cause of stress concentration, induced high crack increase rate, affect the safety and usage of hydroelectric power plant. Stress distribution analysis is a very important and essential surveying technique to analyze bi-material and singular point problems. The finite difference infinitely small element method has been demonstrated, suitable for analyzing the buckling phenomena of welding seam and steel plate with crack. Especially, this method can easily analyze the singularity of kink crack. Nevertheless, the construction form and deformation shape of some gates are three-dimensional system. Therefore, the three-dimensional Digital Image Correlation (DIC) has been developed and applied to analyze the strain variation of steel plate with crack at weld joint. The proposed Digital image correlation (DIC) technique is an only non-contact method for measuring the variation of test object. According to rapid development of digital camera, the cost of this digital image correlation technique has been reduced. Otherwise, this DIC method provides with the advantages of widely practical application of indoor test and field test without the restriction on the size of test object. Thus, the research purpose of this research is to develop and apply this technique to monitor mechanics crack variations of weld steel hydraulic gate and its conformation under action of loading. The imagines can be picked from real time monitoring process to analyze the strain change of each loading stage. The proposed 3-Dimensional digital image correlation method, developed in the study, is applied to analyze the post-buckling phenomenon and buckling tendency of welded steel plate with crack. Then, the stress intensity of 3-dimensional analysis of different materials and enhanced materials in steel plate has been analyzed in this paper. The test results show that this proposed three-dimensional DIC method can precisely detect the crack variation of welded steel plate under different loading stages. Especially, this proposed DIC method can detect and identify the crack position and the other flaws of the welded steel plate that the traditional test methods hardly detect these kind phenomena. Therefore, this proposed three-dimensional DIC method can apply to observe the mechanics phenomena of composite materials subjected to loading and operating.

Keywords: welded steel plate, crack variation, three-dimensional digital image correlation (DIC), crack stel plate

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Authors: R. P. Hewawasam, A. F. Dulhunty

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The ryanodine receptor (RyR) is an intracellular ion channel that releases Ca2+ from the sarcoplasmic reticulum and is essential for the excitation-contraction coupling and contraction in striated muscle. Human muscle specific glutathione transferase M2-2 (GSTM2-2) is a highly specific inhibitor of cardiac ryanodine receptor (RyR2) activity. Single channel-lipid bilayer studies and Ca2+ release assays performed using the C-terminal half of the GSTM2-2 and its mutants F157A and Y160A confirmed the ability of the C terminal domain of GSTM2-2 to specifically inhibit the cardiac ryanodine receptor activity. Objective of the present study is to determine the effect of C terminal domain of GSTM2-2 (GSTM2-2C) and the mutants, F157A and Y160A on the Ca2+ transients of neonatal ventricular cardiomyocytes. Primary cardiomyocytes were cultured from neonatal rats. They were treated with GSTM2-2C and the two mutants F157A and Y160A at 15µM and incubated for 2 hours. Then the cells were led with Fluo-4AM, fluorescent Ca2+ indicator, and the field stimulated (1 Hz, 3V and 2ms) cells were excited using the 488 nm argon laser. Contractility of the cells were measured and the Ca2+ transients in the stained cells were imaged using Leica SP5 confocal microscope. Peak amplitude of the Ca2+ transient, rise time and decay time from the peak were measured for each transient. In contrast to GSTM2C which significantly reduced the % shortening (42.8%) in the field stimulated cells, F157A and Y160A failed to reduce the % shortening.Analysis revealed that the average amplitude of the Ca2+ transient was significantly reduced (P<0.001) in cells treated with the wild type GSTM2-2C compared to that of untreated cells. Cells treated with the mutants F157A and Y160A didn’t change the Ca2+ transient significantly compared to the control. A significant increase in the rise time (P< 0.001) and a significant reduction in the decay time (P< 0.001) were observed in cardiomyocytes treated with GSTM2-2C compared to the control but not with F157A and Y160A. These results are consistent with the observation that GSTM2-2C reduced the Ca2+ release from the cardiac SR significantly whereas the mutants, F157A and Y160A didn’t show any effect compared to the control. GSTM2-2C has an isoform-specific effect on the cardiac ryanodine receptor activity and also it inhibits RyR2 channel activity only during diastole. Selective inhibition of RyR2 by GSTM2-2C has significant clinical potential in the treatment of cardiac arrhythmias and heart failure. Since GSTM2-2C-terminal construct has no GST enzyme activity, its introduction to the cardiomyocyte would not exert any unwanted side effects that may alter its enzymatic action. The present study further confirms that GSTM2-2C is capable of decreasing the Ca2+ release from the cardiac SR during diastole. These results raise the future possibility of using GSTM2-2C as a template for therapeutics that can depress RyR2 function when the channel is hyperactive in cardiac arrhythmias and heart failure.

Keywords: arrhythmia, cardiac muscle, cardiac ryanodine receptor, GSTM2-2

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Authors: Mitali Saha, Soma Das

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The fabrication of nanoscale materials for use in chemical sensing, biosensing and biological analyses has proven a promising avenue in the last few years. Cholesterol has aroused considerable interest in recent years on account of its being an important parameter in clinical diagnosis. There is a strong positive correlation between high serum cholesterol level and arteriosclerosis, hypertension, and myocardial infarction. Enzyme-based electrochemical biosensors have shown high selectivity and excellent sensitivity, but the enzyme is easily denatured during its immobilization procedure and its activity is also affected by temperature, pH, and toxic chemicals. Besides, the reproducibility of enzyme-based sensors is not very good which further restrict the application of cholesterol biosensor. It has been demonstrated that carbon nanotubes could promote electron transfer with various redox active proteins, ranging from cytochrome c to glucose oxidase with a deeply embedded redox center. In continuation of our earlier work on the synthesis and applications of carbon and metal based nanoparticles, we have reported here the synthesis of carbon nanotubes (CCNT) by burning coconut oil under insufficient flow of air using an oil lamp. The soot was collected from the top portion of the flame, where the temperature was around 6500C which was purified, functionalized and then characterized by SEM, p-XRD and Raman spectroscopy. The SEM micrographs showed the formation of tubular structure of CCNT having diameter below 100 nm. The XRD pattern indicated the presence of two predominant peaks at 25.20 and 43.80, which corresponded to (002) and (100) planes of CCNT respectively. The Raman spectrum (514 nm excitation) showed the presence of 1600 cm-1 (G-band) related to the vibration of sp2-bonded carbon and at 1350 cm-1 (D-band) responsible for the vibrations of sp3-bonded carbon. A nonenzymatic cholesterol biosensor was then fabricated on an insulating Teflon material containing three silver wires at the surface, covered by CCNT, obtained from coconut oil. Here, CCNTs worked as working as well as counter electrodes whereas reference electrode and electric contacts were made of silver. The dimensions of the electrode was 3.5 cm×1.0 cm×0.5 cm (length× width × height) and it is ideal for working with 50 µL volume like the standard screen printed electrodes. The voltammetric behavior of cholesterol at CCNT electrode was investigated by cyclic voltammeter and differential pulse voltammeter using 0.001 M H2SO4 as electrolyte. The influence of the experimental parameters on the peak currents of cholesterol like pH, accumulation time, and scan rates were optimized. Under optimum conditions, the peak current was found to be linear in the cholesterol concentration range from 1 µM to 50 µM with a sensitivity of ~15.31 μAμM−1cm−2 with lower detection limit of 0.017 µM and response time of about 6s. The long-term storage stability of the sensor was tested for 30 days and the current response was found to be ~85% of its initial response after 30 days.

Keywords: coconut oil, CCNT, cholesterol, biosensor

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Authors: John Mark Payawal, Francis Aldrine Uy, John Paul Carreon

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This paper shows the application of Structural Health Monitoring, SHM into bridges. Bridges are structures built to provide passage over a physical obstruction such as rivers, chasms or roads. The Philippines has a total of 8,166 national bridges as published on the 2015 atlas of the Department of Public Works and Highways (DPWH) and only 2,924 or 35.81% of these bridges are in good condition. As a result, PHP 30.464 billion of the 2016 budget of DPWH is allocated on roads and/or bridges maintenance alone. Intensive spending is owed to the present practice of outdated manual inspection and assessment, and poor structural health monitoring of Philippine infrastructures. As the School of Civil, Environmental, & Geological Engineering of Mapua Institute of Technology (MIT) continuous its well driven passion in research based projects, a partnership with the Department of Science and Technology (DOST) and the DPWH launched the application of Structural Health Monitoring, (SHM) in Padre Jacinto Zamora Flyover. The flyover is located along Nagtahan Boulevard in Sta. Mesa, Manila that connects Brgy. 411 and Brgy. 635. It gives service to vehicles going from Lacson Avenue to Mabini Bridge passing over Legarda Flyover. The flyover is chosen among the many located bridges in Metro Manila as the focus of the pilot testing due to its site accessibility, and complete structural built plans and specifications necessary for SHM as provided by the Bureau of Design, BOD department of DPWH. This paper focuses on providing a method to calibrate theoretical readings from STAAD Vi8 Pro and sync the data to actual MEMS accelerometer readings. It is observed that while the design standards used in constructing the flyover was reflected on the model, actual readings of MEMS accelerometer display a large difference compared to the theoretical data ran and taken from STAAD Vi8 Pro. In achieving a true seismic response of the modeled bridge or hence syncing the theoretical data to the actual sensor reading also called as the independent variable of this paper, analysis using single degree of freedom (SDOF) of the flyover under free vibration without damping using STAAD Vi8 Pro is done. The earthquake excitation and bridge responses are subjected to earthquake ground motion in the form of ground acceleration or Peak Ground Acceleration, PGA. Translational acceleration load is used to simulate the ground motion of the time history analysis acceleration record in STAAD Vi8 Pro.

Keywords: accelerometer, analysis using single degree of freedom, micro electro mechanical system, peak ground acceleration, structural health monitoring

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Authors: Lishuang Ma

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Charge transfer (CT) complex, also known as Electron donor-acceptor (EDA) complex, has received attentions increasingly in the field of synthetic chemistry community, due to the CT complex can absorb the visible light through the intermolecular charge transfer excited states, various of catalyst-free photochemical transformations under mild visible-light conditions. However, a number of fundamental questions are still ambiguous, such as the origin of visible light absorption, the photochemical and photophysical properties of the CT complex, as well as the detailed mechanism of the radical coupling pathways mediated by CT complex. Since these are critical factors for target-specific design and synthesis of more new-type CT complexes. To this end, theoretical investigations were performed in our group to answer these questions based on multiconfigurational perturbation theory. The photo-induced fluoroalkylation reactions are mediated by CT complexes, which are formed by the association of an acceptor of perfluoroalkyl halides RF−X (X = Br, I) and a suitable donor molecule such as β-naphtholate anion, were chosen as a paradigm example in this work. First, spectrum simulations were carried out by both CASPT2//CASSCF/PCM and TD-DFT/PCM methods. The computational results showed that the broadening spectra in visible light range (360-550nm) of the CT complexes originate from the 1(σπ*) excitation, accompanied by an intermolecular electron transfer, which was also found closely related to the aggregate states of the donor and acceptor. Moreover, from charge translocation analysis, the CT complex that showed larger charge transfer in the round state would exhibit smaller charge transfer in excited stated of 1(σπ*), causing blue shift relatively. Then, the excited-state potential energy surface (PES) was calculated at CASPT2//CASSCF(12,10)/ PCM level of theory to explore the photophysical properties of the CT complexes. The photo-induced C-X (X=I, Br) bond cleavage was found to occur in the triplet state, which is accessible through a fast intersystem crossing (ISC) process that is controlled by the strong spin-orbit coupling resulting from the heavy iodine and bromine atoms. Importantly, this rapid fragmentation process can compete and suppress the backward electron transfer (BET) event, facilitating the subsequent effective photochemical transformations. Finally, the reaction pathways of the radical coupling were also inspected, which showed that the radical chain propagation pathway could easy to accomplish with a small energy barrier no more than 3.0 kcal/mol, which is the key factor that promote the efficiency of the photochemical reactions induced by CT complexes. In conclusion, theoretical investigations were performed to explore the photophysical and photochemical properties of the CT complexes, as well as the mechanism of radical coupling reactions mediated by CT complex. The computational results and findings in this work can provide some critical insights into mechanism-based design for more new-type EDA complexes

Keywords: charge transfer complex, electron transfer, multiconfigurational perturbation theory, radical coupling

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