Sample records for chromatography theoretical investigations

  1. Electrochemically modulated liquid chromatography: Theoretical investigations and applications from the perspectives of chromatography and interfacial electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Keller, David W.


    Electrochemically modulated liquid chromatography (EMLC) employs a conductive material as both a stationary phase for chromatographic separations and as a working electrode for performing electrochemistry experiments. This dual functionality gives EMLC the capacity to manipulate chromatographic separations by changing the potential applied (E{sub app}) to the stationary phase with respect to an external reference. The ability to monitor retention as a function of E{sub app} provides a means to chromatographically monitor electrosorption processes at solid-liquid interfaces. In this dissertation, the retention mechanism for EMLC is examined from the perspective of electrical double layer theory and interfacial thermodynamics. From the chromatographic data, it is possible to determine the interfacial excess ({Lambda}) of a solute and changes in interfacial tension (d{gamma}) as a function of both E{sub app} and the supporting electrolyte concentration. Taken together, these two experimentally manipulated parameters can be examined within the context of the Gibbs adsorption equation to delineate the contribution of a variety of interfacial properties, including the charge of solute on the stationary phase and the potential of zero charge (PZC), to the mechanism behind EMLC-based retention. The chromatographic probing of interfacial phenomena is complemented by electroanalytical experiments that exploit the ability to monitor the electronic current flowing through an EMLC column. Cyclic voltammetry and chronoamperometry of an EMLC column are used to determine the electronic performance characteristics of an EMLC column. An electrochemical flow injection analysis of a column is provided in which the current required to maintain a constant E{sub app} is monitored and provides a way to examine the influence that acetonitrile and supporting electrolyte composition, flow rate, column backpressure, and ionic strength have on the structure of electrified interfaces.

  2. Electrochemically modulated liquid chromatography: Theoretical investigations and applications from the perspectives of chromatography and interfacial electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Keller, David W. [Iowa State Univ., Ames, IA (United States)


    Electrochemically modulated liquid chromatography (EMLC) employs a conductive material as both a stationary phase for chromatographic separations and as a working electrode for performing electrochemistry experiments. This dual functionality gives EMLC the capacity to manipulate chromatographic separations by changing the potential applied (Eapp) to the stationary phase with respect to an external reference. The ability to monitor retention as a function of Eapp provides a means to chromatographically monitor electrosorption processes at solid-liquid interfaces. In this dissertation, the retention mechanism for EMLC is examined from the perspective of electrical double layer theory and interfacial thermodynamics. From the chromatographic data, it is possible to determine the interfacial excess (Λ) of a solute and changes in interfacial tension (dγ) as a function of both Eapp and the supporting electrolyte concentration. Taken together, these two experimentally manipulated parameters can be examined within the context of the Gibbs adsorption equation to delineate the contribution of a variety of interfacial properties, including the charge of solute on the stationary phase and the potential of zero charge (PZC), to the mechanism behind EMLC-based retention. The chromatographic probing of interfacial phenomena is complemented by electroanalytical experiments that exploit the ability to monitor the electronic current flowing through an EMLC column. Cyclic voltammetry and chronoamperometry of an EMLC column are used to determine the electronic performance characteristics of an EMLC column. An electrochemical flow injection analysis of a column is provided in which the current required to maintain a constant Eapp is monitored and provides a way to examine the influence that acetonitrile and supporting electrolyte composition, flow rate, column backpressure, and ionic strength have on the structure of electrified interfaces.


    Institute of Scientific and Technical Information of China (English)

    YANGGengliang; TAOZuyi


    The unified theoretical moment expressions for elution chromatography and frontal chromatography when the sorption process is described by a linear model were derived. The moment expressions derived by previous authors can be obtained from these unified theoretical moment expressions. In this paper, a mathematical analysis has been carried out so as to set up a unified theoretical basis for elution and frontal chromatography.

  4. Student Investigations Using Chromatography (United States)

    Witters, Weldon L.; Bush, Kenneth


    Three different problems are given for student investigation in determining amino acid compositions, floral pigments, and water soluble amino acids by using the techniques of Roll Chromotography, DISC Chromotography, Thin Layer, and Paper Chromotography. (BR)

  5. Theoretical investigation of exchange bias

    Institute of Scientific and Technical Information of China (English)

    Xiong Zhi-Jie; Wang Huai-Yu; Ding Ze-Jun


    The exchange bias of bilayer magnetic films consisting of ferromagnetic (FM) and antiferromagnetic (AFM) layers in an uncompensated case is studied by use of the many-body Green's function method of quantum statistical theory.The effects of the layer thickness and temperature and the interfacial coupling strength on the exchange bias HE are investigated. The dependence of the exchange bias HE on the FM layer thickness and temperature is qualitatively in agreement with experimental results. When temperature varies, both the coercivity HC and HE decrease with the temperature increasing. For each FM thickness, there exists a least AFM thickness in which the exchange bias occurs,which is called pinning thickness.

  6. Theoretical Investigations of Chaotic Dynamics (United States)


    INVESTIGATIONS OF CHAOTIC DYNAMICS" PROFESSOR JAMES A YORKE CELSO GREBOGI UNIVERSITY OF MARYLAND COLLEGE PARK MD 20742-2431 F49620-92-J-0033 I PREFACE This...publication. d. "Evolution of Attractor Boundaries of Two-Dimensional Noninvertible Maps", W. Chin, I. Kan and C. Grebogi , Random & Comp. Dyn. L 349-370...1993). e "How often are chaotic saddles nonhyperbolic?", Y-C. Lai, C. Grebogi , and J. A Yorke, Nonlinearity, 6., 779-797 (1993). f. "A Geometric

  7. Theoretical study of rock mass investigation efficiency

    Energy Technology Data Exchange (ETDEWEB)

    Holmen, Johan G.; Outters, Nils [Golder Associates, Uppsala (Sweden)


    The study concerns a mathematical modelling of a fractured rock mass and its investigations by use of theoretical boreholes and rock surfaces, with the purpose of analysing the efficiency (precision) of such investigations and determine the amount of investigations necessary to obtain reliable estimations of the structural-geological parameters of the studied rock mass. The study is not about estimating suitable sample sizes to be used in site investigations.The purpose of the study is to analyse the amount of information necessary for deriving estimates of the geological parameters studied, within defined confidence intervals and confidence level In other words, how the confidence in models of the rock mass (considering a selected number of parameters) will change with amount of information collected form boreholes and surfaces. The study is limited to a selected number of geometrical structural-geological parameters: Fracture orientation: mean direction and dispersion (Fisher Kappa and SRI). Different measures of fracture density (P10, P21 and P32). Fracture trace-length and strike distributions as seen on horizontal windows. A numerical Discrete Fracture Network (DFN) was used for representation of a fractured rock mass. The DFN-model was primarily based on the properties of an actual fracture network investigated at the Aespoe Hard Rock Laboratory. The rock mass studied (DFN-model) contained three different fracture sets with different orientations and fracture densities. The rock unit studied was statistically homogeneous. The study includes a limited sensitivity analysis of the properties of the DFN-model. The study is a theoretical and computer-based comparison between samples of fracture properties of a theoretical rock unit and the known true properties of the same unit. The samples are derived from numerically generated boreholes and surfaces that intersect the DFN-network. Two different boreholes are analysed; a vertical borehole and a borehole that is

  8. Theoretical and experimental investigations of Chinese evacuated tubular solar collectors

    DEFF Research Database (Denmark)

    Qin, Lin; Furbo, Simon


    Four different marketed Chinese evacuated tubular solar collectors have been investigated both theoretically and experimentally. The advantages of the investigated solar collectors compared to normal flat plate collectors were elucidated.......Four different marketed Chinese evacuated tubular solar collectors have been investigated both theoretically and experimentally. The advantages of the investigated solar collectors compared to normal flat plate collectors were elucidated....

  9. Theoretical and Experimental Investigation of Heterojunction Interfaces (United States)


    Ge grown on substrates of (111), (110), and (100) GaAs have been Investigated with x-ray photoelectron spectos - copy. Observed changes in core-level...determinations were made on each interface. In all cases, measure- ment reproducibility was ɘ.01 eV and was usual- ly ɘ.005 eV; calibration uncertainties...0.01 eV and in most cases it was < ±0.005 eV. Calibration uncertainties increase the total error limits for AEg to ±0.01 eV In the table, we also list

  10. Chromatography. (United States)

    Brantley, L. Reed, Sr.; Demanche, Edna L.; Klemm, E. Barbara; Kyselka, Will; Phillips, Edwin A.; Pottenger, Francis M.; Yamamoto, Karen N.; Young, Donald B.

    This booklet presents some activities on chromatography. Directions for preparing leaf pigment extracts using alcohol are given, and paper chromatography and thin-layer chromatography are described as modifications of the basic principles of chromatography. (KHR)

  11. Supercritical Fluid Chromatography--Theoretical Background and Applications on Natural Products. (United States)

    Hartmann, Anja; Ganzera, Markus


    The use of supercritical fluid chromatography for natural product analysis as well as underlying theoretical mechanisms and instrumental requirements are summarized in this review. A short introduction focusing on the historical development of this interesting separation technique is followed by remarks on the current instrumental design, also describing possible detection modes and useable stationary phases. The overview on relevant applications is grouped based on their basic intention, may it be (semi)preparative or purely analytical. They indicate that supercritical fluid chromatography is still primarily considered for the analysis of nonpolar analytes like carotenoids, fatty acids, or terpenes. The low polarity of supercritical carbon dioxide, which is used with modifiers almost exclusively as a mobile phase today, combined with high efficiency and fast separations might explain the popularity of supercritical fluid chromatography for the analysis of these compounds. Yet, it has been shown that more polar natural products (e.g., xanthones, flavonoids, alkaloids) are separable too, with the same (if not superior) selectivity and reproducibility than established approaches like HPLC or GC.

  12. Experimental and theoretical investigation of high gradient acceleration

    Energy Technology Data Exchange (ETDEWEB)

    Bekefi, G.; Chen, C.; Chen, S.; Danly, B.; Temkin, R.J.; Wurtele, J.S.


    This report contains a technical progress summary of the research conducted under the auspices of DOE Grant No. DE-FG0291ER-40648. Experimental and Theoretical Investigations of High Gradient Acceleration.'' This grant supports three research tasks: Task A consists of the design and fabrication of a 17GHz of photocathode gun, Task B supports the testing of high gradient acceleration using a 33GHz structure, and Task C comprises theoretical investigations, both in support of the experimental tasks and on critical physics issues for the development of high energy linear colliders. This report is organized as follows. The development of an rf gun design and research progress on the picosecond laser system is summarized in Sec. 2, the status of the studies of the LBL/Haimson high gradient structure, using a 50 MW free-electron laser is summarized in Sec. 3, and theoretical research progress is described in Sec. 4. Supporting material is contained in Appendices A-G.

  13. Some theoretical and practical aspects in the separation of humic substances by combined liquid chromatography methods. (United States)

    Hutta, Milan; Góra, Róbert; Halko, Radoslav; Chalányová, Mária


    Permanent need to understand nature, structure and properties of humic substances influences also separation methods that are in a wide scope used for fractionation, characterization and analysis of humic substances (HS). At the first glance techniques based on size-exclusion phenomena are the most useful and utilized for relating elution data to the molecular mass distribution of HS, however, with some limitations and exceptions, respectively, in the structural investigation of HS. The second most abundant separation mechanism is reversed-phase based on weak hydrophobic interactions beneficially combined with the step gradients inducing distinct features in rather featureless analytical signal of HS. Relatively great effort is invested to the developments of immobilized-metal affinity chromatography mimicking chelate-forming properties of HS as ligands in the environment. Surprisingly, relatively less attention is given to the ion-ion interactions based ion-exchange chromatography of HS. Chromatographic separation methods play also an important role in the examination of interactions of HS with pesticides. They allow us to determine binding constants and the other data necessary to predict the mobility of chemical pollutants in the environment. HS is frequently adversely acting in analytical procedures as interfering substance, so more detailed information is desired on manifestation of its numerous properties in analytical procedures. The article topic is covered by the review emphasizing advances in the field done in the period of last 10 years from 2000 till 2010.

  14. Challenges in the theoretical investigations of lipid membrane configurations

    Institute of Scientific and Technical Information of China (English)

    Tu Zhan-Chun


    We report some key results in the theoretical investigations of configurations of lipid membranes and present several challenges in this field,which involve (i) the exact solutions to the shape equation of lipid vesicles,(ii) the exact solutions to the governing equations of open lipid membranes,(iii) the neck condition of two-phase vesicles in the budding state,(iv)the nonlocal theory of membrane elasticity,and (v) the relationship between the symmetry and the magnitude of the free energy.

  15. Determination of theoretical retention times for peptides analyzed by reversed- -phase high-performance liquid chromatography

    Directory of Open Access Journals (Sweden)

    Jerzy Dziuba


    Full Text Available   Background. Peptides are important components of foods mainly due to their biological activity. The basic method of their identification is reversed phase high-performance liquid chromatography coupled with electrospray-ionization mass spectrometry (RP-HPLC-ESI-MS. Retention time (tR prediction in silico is very helpful in analysis of multicomponent peptide mixtures. One of problems associated with RP-HPLC-ESI-MS is deterioration of mass spectra quality by trifluoroacetic acid (TFA. This problem can be avoided through the use of chromatographic columns designed for work with low TFA concentrations in mobile phase. The objective of this study was to determine the correlations between peptide retention times predicted with the use of a program available on-line and experimental retention times obtained using the column working with low TFA concentrations. Material and methods. The set of synthetic peptides and bovine α-lactalbumin fragments (18 peptides was used in the experiment. Theoretical retention times were calculated using Sequence Specific Retention Calculator (SSRC program. The experimental retention times were measured via RP-HPLC-ESI-MS method using column working with low TFA content. The dependence between theoretical and experimental tR was expressed via empirical equations. Results. The best correlation between theoretical and experimental retention times of peptides containing at least four amino acid residues has been obtained when third order polynomial (R² = 0.9536. Prediction quality for di- and tripeptides was significantly lower. The method described can be applied for cysteine-containing peptides although our sample preparation procedure did not include modification of this amino acid, taken into attention by SSRC program. Conclusions. The results of this study validate the usefulness of a third degree polynomial as a simple function describing the correlation between peptide retention times predicted by an on

  16. Theoretical Investigation of Trust in Small and Medium Sized Enterprises

    Directory of Open Access Journals (Sweden)

    Valentinas Navickas


    Full Text Available The hectic pace of competition pushes the sector of small and medium enterprise to adopt sophisticated marketing ideas. In this context, customers are becoming more and more selective. However, expansion possibilities are burdened by the great variety of limitations. The current study paper aims to investigate the academic perception of trust which is treated as competitive advantage for small and medium enterprises. The object of the article is trust in small and medium enterprises. It has three objectives: to analyse small and medium enterprise characteristics through the academic perspective; to consider trust from the theoretical point of view; and to present the models that centre their attention on the trust as a construct that enhances customer satisfaction. Regarding the novelty of the current study, it brings a novel approach on a great variety of collected understandings of trust and puts an important foundation for future theory and practice investigations.

  17. An Experimental and Theoretical Investigation of Electrostatically Coupled Cantilever Microbeams

    KAUST Repository

    Ilyas, Saad


    We present an experimental and theoretical investigation of the static and dynamic behavior of electrostatically coupled laterally actuated silicon microbeams. The coupled beam resonators are composed of two almost identical flexible cantilever beams forming the two sides of a capacitor. The experimental and theoretical analysis of the coupled system is carried out and compared against the results of beams actuated with fixed electrodes individually. The pull-in characteristics of the electrostatically coupled beams are studied, including the pull-in time. The dynamics of the coupled dual beams are explored via frequency sweeps around the neighborhood of the natural frequencies of the system for different input voltages. Good agreement is reported among the simulation results and the experimental data. The results show considerable drop in the pull-in values as compared to single microbeam resonators. The dynamics of the coupled beam resonators are demonstrated as a way to increase the bandwidth of the resonator near primary resonance as well as a way to introduce increased frequency shift, which can be promising for resonant sensing applications. Moreover the dynamic pull-in characteristics are also studied and proposed as a way to sense the shift in resonance frequency.

  18. Investigations on Actuator Dynamics through Theoretical and Finite Element Approach

    Directory of Open Access Journals (Sweden)

    Somashekhar S. Hiremath


    Full Text Available This paper gives a new approach for modeling the fluid-structure interaction of servovalve component-actuator. The analyzed valve is a precision flow control valve-jet pipe electrohydraulic servovalve. The positioning of an actuator depends upon the flow rate from control ports, in turn depends on the spool position. Theoretical investigation is made for No-load condition and Load condition for an actuator. These are used in finite element modeling of an actuator. The fluid-structure-interaction (FSI is established between the piston and the fluid cavities at the piston end. The fluid cavities were modeled with special purpose hydrostatic fluid elements while the piston is modeled with brick elements. The finite element method is used to simulate the variation of cavity pressure, cavity volume, mass flow rate, and the actuator velocity. The finite element analysis is extended to study the system's linearized response to harmonic excitation using direct solution steady-state dynamics. It was observed from the analysis that the natural frequency of the actuator depends upon the position of the piston in the cylinder. This is a close match with theoretical and simulation results. The effect of bulk modulus is also presented in the paper.

  19. Experimental and Theoretical Investigations of Wet Flue Gas Desulphurisation

    DEFF Research Database (Denmark)

    Kiil, Søren

    limestones of dif-ferent origin were tested. A transient, mass transport controlled, mathematical model was de-veloped to describe the dissolution process. Model predictions were found to be qualitatively in good agreement with experimental data. Deviations between measurements and simulations were......-scale experiments. In the theoretical part of the work, the laboratory and pilot plant observations are investigated using mathematical modelling.The mechanism underlying the rate of dissolution of finely grinded limestone particles was examined in a laboratory batch apparatus using acid titration. Three Danish...... attributed primarily to the particle size distribution (PSD) measurements of the limestone particles, which were used as model inputs. The measured PSD was probably not representa-tive of a given limestone sample because of agglomeration phenomena taking place in the dis-perser, preventing a stable...


    Directory of Open Access Journals (Sweden)

    M. V. Shumanova


    Full Text Available To the salting process of fish many studies are devoted, both in experimental and in theoretical terms. Study of features of fish salting in historical terms can be divided into 3 groups. One group of researchers believes that osmotic pressure has a major influence during the salting process. Another group attributed this process to the influence of molecular diffusion. The third group considers that during this process takes place both osmosis and diffusion. Determination of the main characteristics (salinity, diffusion coefficients, time of salting, etc. is a very time-consuming task. This leads to the idea of searching for innovative research methods. Current state of science, in addition to theoretical solutions points to the possibility to determine the basic characteristics of salting and applying methods associated with the interaction of ultrasound and electromagnetic radiation with matter. In our studies, we have been producing laser beam scanning of salt solution and fish meat thickness. Scattered radiation is determined by the salt concentration, diffusion coefficients, the size of the diffusing particles. This method is called a photon correlation spectroscopy. It has been applied in our work. The dependence of the scattered light intensity on the concentration of sodium chloride solution (brine has been investigated. According to diffusion coefficient a diffusion in solution to herring skin a conclusion was made that salt solution obtains fractal structure and its size was determined. Also we determined diffusion coefficients depending on the temperature in the layers. The layers are brine-leather, leather, and herring meat thickness. The process of diffusion-osmotic equilibrium revealed at temperatures of 10-12 ° C. Suggested the possibility of higher quality of fish salting at low temperatures. On the basis of the selfsimilar solution of the differential diffusion equation, a formula for calculating time salting fish was obtained

  1. Theoretical and experimental investigation of multispectral photoacoustic osteoporosis detection method (United States)

    Steinberg, Idan; Hershkovich, Hadas Sara; Gannot, Israel; Eyal, Avishay


    Osteoporosis is a widespread disorder, which has a catastrophic impact on patients lives and overwhelming related to healthcare costs. Recently, we proposed a multispectral photoacoustic technique for early detection of osteoporosis. Such technique has great advantages over pure ultrasonic or optical methods as it allows the deduction of both bone functionality from the bone absorption spectrum and bone resistance to fracture from the characteristics of the ultrasound propagation. We demonstrated the propagation of multiple acoustic modes in animal bones in-vitro. To further investigate the effects of multiple wavelength excitations and of induced osteoporosis on the PA signal a multispectral photoacoustic system is presented. The experimental investigation is based on measuring the interference of multiple acoustic modes. The performance of the system is evaluated and a simple two mode theoretical model is fitted to the measured phase signals. The results show that such PA technique is accurate and repeatable. Then a multiple wavelength excitation is tested. It is shown that the PA response due to different excitation wavelengths revels that absorption by the different bone constitutes has a profound effect on the mode generation. The PA response is measured in single wavelength before and after induced osteoporosis. Results show that induced osteoporosis alters the measured amplitude and phase in a consistent manner which allows the detection of the onset of osteoporosis. These results suggest that a complete characterization of the bone over a region of both acoustic and optical frequencies might be used as a powerful tool for in-vivo bone evaluation.

  2. Experimental Investigation and Theoretical Modeling of Nanosilica Activity in Concrete

    Directory of Open Access Journals (Sweden)

    Han-Seung Lee


    Full Text Available This paper presents experimental investigations and theoretical modeling of the hydration reaction of nanosilica blended concrete with different water-to-binder ratios and different nanosilica replacement ratios. The developments of chemically bound water contents, calcium hydroxide contents, and compressive strength of Portland cement control specimens and nanosilica blended specimens were measured at different ages: 1 day, 3 days, 7 days, 14 days, and 28 days. Due to the pozzolanic reaction of nanosilica, the contents of calcium hydroxide in nanosilica blended pastes are considerably lower than those in the control specimens. Compared with the control specimens, the extent of compressive strength enhancement in the nanosilica blended specimens is much higher at early ages. Additionally, a blended cement hydration model that considers both the hydration reaction of cement and the pozzolanic reaction of nanosilica is proposed. The properties of nanosilica blended concrete during hardening were evaluated using the degree of hydration of cement and the reaction degree of nanosilica. The calculated chemically bound water contents, calcium hydroxide contents, and compressive strength were generally consistent with the experimental results.

  3. Investigation of Pinus mugo essential oil oxygenated fraction by combined use of gas chromatography and dry column chromatography. (United States)

    A, M B; Coran, S A; Giannellini, V; Vincieri, F F; Moneti, G


    The oxygenated compounds of Pinus mugo Turra essential oil were investigated by a combination of GC and dry column chromatography (DCC) coordinated by GC data processing. The collected data resulted in a bar graph ("normalized" gas chromatogram) giving the RRT's and relative amounts of 68 components; 38 of them were identified by MS and IR. The described procedure may be used for essential oil analysis in general.

  4. A Theoretical Study of the Separation Principle in Size Exclusion Chromatography

    DEFF Research Database (Denmark)

    Wang, Yanwei; Teraoka, Iwao; Hansen, Flemming Yssing


    The principle of polymer separation in size exclusion chromatography (SEC) is studied based on a classical equilibrium partitioning theory. The task is to examine the correlation between the mean span dimension of polymer chains and their equilibrium partition coefficients with confining pores...

  5. An empirical investigation of theoretical loss and gambling intensity. (United States)

    Auer, Michael; Griffiths, Mark D


    Many recent studies of internet gambling-particularly those that have analysed behavioural tracking data-have used variables such 'bet size' and 'number of games played' as proxy measures for 'gambling intensity'. In this paper it is argued that the most stable and reliable measure for 'gambling intensity' is the 'theoretical loss' (a product of total bet size and house advantage). In the long run, the theoretical loss corresponds with the Gross Gaming Revenue generated by commercial gaming operators. For shorter periods of time, theoretical loss is the most stable measure of gambling intensity as it is not distorted by gamblers' occasional wins. Even for single bets, the theoretical loss reflects the amount a player is willing to risk. Using behavioural tracking data of 100,000 players who played online casino, lottery and/or poker games, this paper also demonstrates that bet size does not equate to or explain theoretical loss as it does not take into account the house advantage. This lack of accuracy is shown to be even more pronounced for gamblers who play a variety of games.

  6. Applying Theoretical Approach for Predicting the Selective Calcium Channel Blockers Pharmacological Parameter by Biopartitioning Micellar Chromatography

    Institute of Scientific and Technical Information of China (English)

    WANG Su-Min; YANG Geng-Liang; LI Zhi-Wei; LIU Hai-Yan; GUO Hui-Juan


    The usefulness of biopartitioning micellar chromatography (BMC) for predicting oral drug acute toxicity and apparent bioavailability was demonstrated. A logarithmic model (an LD50 model) and the second order polynomial models (apparent bioavailability model) have been obtained using the retention data of the selective calcium channel blockers to predict pharmacological properties of compounds. The use of BMC is simple, reproducible and can provide key information about the acute toxicity and transport properties of new compounds during the drug discovery process.

  7. Two-dimensional liquid chromatography and its application in traditional Chinese medicine analysis and metabonomic investigation. (United States)

    Li, Zheng; Chen, Kai; Guo, Meng-zhe; Tang, Dao-quan


    Two-dimensional liquid chromatography has become an attractive analytical tool for the separation of complex samples due to its enhanced selectivity, peak capacity, and resolution compared with one-dimensional liquid chromatography. Recently, more attention has been drawn on the application of this separation technique in studies concerning traditional Chinese medicines, metabonomes, proteomes, and other complex mixtures. In this review, we aim to examine the application of two-dimensional liquid chromatography in traditional Chinese medicine analysis and metabonomic investigation. The classification and evaluation indexes were first introduced. Then, various switching methods were summarized when used in an on-line two-dimensional liquid chromatography system. Finally, the applications of this separation technique in traditional Chinese medicine analysis and metabonomic investigation were discussed on the basis of specific studies.

  8. Investigations in Experimental and Theoretical High Energy Physics

    Energy Technology Data Exchange (ETDEWEB)

    Krennrich, Frank [Iowa State University


    We report on the work done under DOE grant DE-FG02-01ER41155. The experimental tasks have ongoing efforts at CERN (ATLAS), the Whipple observatory (VERITAS) and R&D work on dual readout calorimetry and neutrino-less double beta decay. The theoretical task emphasizes the weak interaction and in particular CP violation and neutrino physics. The detailed descriptions of the final report on each project are given under the appropriate task section of this report.

  9. Theoretical investigation on the Schelling's critical neighborhood demand

    CERN Document Server

    Shin, Jae Kyun


    We derived the critical neighborhood demand in the Schelling's segregation model by studying the conditions for which a chain reaction of migrations of unsatisfied agents occurs. The essence of Schelling dynamics was approximated in two simplified models: (1) a random walk model for the initial stage of the migrations to illustrate the power-law behavior of chain reaction lengths under critical conditions, and (2) a two-room model for the whole process to represent a non-spatial version of segregation dynamics in the Schelling model. Our theoretical results showed good agreements with numerical results obtained from agent-based simulations.

  10. Theoretical investigation on the Schelling's critical neighborhood demand (United States)

    Shin, Jae Kyun; Sayama, Hiroki


    We derived the critical neighborhood demand in the Schelling's segregation model by studying the conditions for which a chain reaction of migrations of unsatisfied agents occurs. The essence of Schelling dynamics was approximated in two simplified models: (1) a random walk model for the initial stage of the migrations to illustrate the power-law behavior of chain reaction lengths under critical conditions, and (2) a two-room model for the whole process to represent a non-spatial version of segregation dynamics in the Schelling model. Our theoretical results showed good agreements with numerical results obtained from agent-based simulations.

  11. Theoretical Investigation on a Novel Hydrodynamic Journal Bearing

    Institute of Scientific and Technical Information of China (English)

    路长厚; 陈淑江; 张建川


    To improve the static and dynamic performance of hydrodynamic journal beatings, a novel bearing is developed, which is a cone-shaped hydrodynamic bearing with spiral oil wedges. The major structural feature of this bearing is the three spiral circular recesses on the beating's surface, leading to improved characteristics. This paper aims to develop a model for design and calculation of the geometric parameters and the oil film thickness, and to provide a theoretical analysis to the static characteristics using a f'mite element method. Some new features are introduced.

  12. Theoretical Investigation of Negative Refraction in Metallic and Ferromagnetic Composites

    Institute of Scientific and Technical Information of China (English)

    SU Hua; LI Cheng-fang


    A new design of LHM (left-handed material) is suggested, in which the wave vector k and the energy flow S (the Poynting vector) are in the opposite direction. Metallic cores or lines are coated with ferromagnetic layers to obtain negative permittivity and permeability. This design may bring some improvements over the binary design, such as higher homogeneity, smaller volume size, lower power loss, higher convenience and economy. The analytical expressions for the permittivity ε and permeability μ are shown to be negative in certain direction and frequency regions. Two specific structures are theoretically discussed and proved to be left-handed.

  13. Combine experimental and theoretical investigation on an alkaloid-Dimethylisoborreverine (United States)

    Singh, Swapnil; Singh, Harshita; Karthick, T.; Agarwal, Parag; Erande, Rohan D.; Dethe, Dattatraya H.; Tandon, Poonam


    A combined experimental (FT-IR, 1H and 13C NMR) and theoretical approach is used to study the structure and properties of antimalarial drug dimethylisoborreverine (DMIB). Conformational analysis, has been performed by plotting one dimensional potential energy curve that was computed using density functional theory (DFT) with B3LYP/6-31G method and predicted conformer A1 as the most stable conformer. After full geometry optimization, harmonic wavenumbers were computed for conformer A1 at the DFT/B3LYP/6-311++G(d,P) level. A complete vibrational assignment of all the vibrational modes have been performed on the bases of the potential energy distribution (PED) and theoretical results were found to be in good agreement with the observed data. To predict the solvent effect, the UV-Vis spectra were calculated in different solvents by polarizable continuum model using TD-DFT method. Molecular docking studies were performed to test the biological activity of the sample using SWISSDOCK web server and Hex 8.0.0 software. The molecular electrostatic potential (MESP) was plotted to identify the reactive sites of the molecule. Natural bond orbital (NBO) analysis was performed to get a deep insight of intramolecular charge transfer. Thermodynamical parameters were calculated to predict the direction of chemical reaction.

  14. Experimental and theoretical investigations on shock wave induced phase transitions (United States)

    Gupta, Satish C.; Sikka, S. K.


    Shock wave loading of a material can cause variety of phase transitions, like polymorphism, amorphization, metallization and molecular dissociations. As the shocked state lasts only for a very short duration (about a few microseconds or less), in-situ microscopic measurements are very difficult. Although such studies are beginning to be possible, most of the shock-induced phase transitions are detected using macroscopic measurements. The microscopic nature of the transition is then inferred from comparison with static pressure data or interpreted by theoretical methods. For irreversible phase transitions, microscopic measurements on recovered samples, together with orientation relations determined from selected area electron diffraction and examination of the morphology of growth of the new phase can provide insight into mechanism of phase transitions. On theoretical side, the current ab initio band structure techniques based on density functional formalism provide capability for accurate computation of the small energy differences (a few mRy or smaller) between different plausible structures. Total energy calculation along the path of a phase transition can furnish estimates of activation barrier, which has implications for understanding kinetics of phase transitions. Molecular dynamics calculations, where the new structure evolves naturally, are becoming increasingly popular especially for understanding crystal to amorphous phase transitions. Illustrations from work at our laboratory will be presented.

  15. Theoretical investigation of real gas effects on Flare and Boattails


    NOMIZO, Kunio; 野溝, 国生


    IN this report, the difference of the pressure coefficient and the drag coefficient between ideal gas and real gas was investigated on flare and boattasls at supersonic speed. For this porpose, the characteristics method was employed. And the difference of the drag coefficient, and the pressure coefficient between ideal gas and real gas was investigated. Also, the difference of the drag coefficient between real gas and the boundary layer was investigated. It has been found that in some region...

  16. Theoretical investigation of nonlinear properties of electrooptical chromophores

    Institute of Scientific and Technical Information of China (English)

    Zhou Yu-fang; Zhuang De-xin


    Organic electrooptical (EO) chromophores are now gaining more attention because the property of organic photorefrative (PR) materials could be controlled by doped EO chromophores. In this paper, nonlinear optical (NLO) properties of a new group of organic electrooptical chromophores, synthesized recently in our laboratory, were elucidated theoretically with the quantum chemical density functional theory (DFT) and the intermediate neglect of differential overlap Hamilton and the configuration interaction (INDO/CI), as well as semiemperical Austin Model 1 (AM1) methods. The electronic transition intensity, dipole moment and the second- order polarizability were obtained. The results show this group of chrormophores possess appropriate optical absorption property and good electrooptical property and optical activity. The second-order polarizabilities βare as large as the order of 10-29 to 10-28 ESU, indicating the promising applications in the future. The physical mechanism of NLO is discussed by means of molecular orbital and electronic charge distribution.


    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Gang; Yang, Jiamin; Zhang, Jiyan; Hu, Zhimin; Zhao, Yang; Qing, Bo; Yang, Guohong; Wei, Minxi; Yi, Rongqing; Song, Tianming; Li, Hang; Yuan, Zheng; Lv, Min [Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China); Meng, Xujun; Xu, Yan; Wu, Zeqing; Yan, Jun, E-mail:, E-mail: [Institute of Applied Physics and Computational Mathematics, Beijing 100088 (China)


    We report on opacity measurements of a silicon (Si) plasma at a temperature of (72 ± 5) eV and a density of (6.0 ± 1.2) mg cm{sup −3} in the photon energy range of 1790–1880 eV. A 23 μg cm{sup −2} Si foil tamped by 50 μg cm{sup −2} CH layers on each side was heated to a hot-dense plasma state by X-ray radiation emitted from a D-shaped gold cavity that was irradiated by intense lasers. Absorption lines of 1s − 2p transitions of Si xiii to Si ix ions have been measured using point-projection spectroscopy. The transmission spectrum of the silicon plasma was determined by comparing the light passing through the plasma to the light from the same shot passing by the plasma. The density of the Si plasma was determined experimentally by side-on radiography and the temperature was estimated from the radiation flux data. Radiative hydrodynamic simulations were performed to obtain the temporal evolutions of the density and temperature of the Si plasma. The experimentally obtained transmission spectra of the Si sample plasma have been reproduced using a detailed term account model with the local thermodynamic equilibrium approximation. The energy levels, oscillator strengths and photoionization cross-sections used in the calculation were generated by the flexible atomic code. The experimental transmission spectrum was compared with the theoretical calculation and good agreement was found. The present experimental spectrum and theoretical calculation were also compared with the new opacities available in the Los Alamos OPLIB database.

  18. [Investigations in dynamics of gauge theories in theoretical particle physics

    Energy Technology Data Exchange (ETDEWEB)


    The major theme of the theoretical physics research conducted under DOE support over the past several years has been within the rubric of the standard model, and concerned the interplay between symmetries and dynamics. The research was thus carried out mostly in the context of gauge field theories, and usually in the presence of chiral fermions. Dynamical symmetry breaking was examined both from the point of view of perturbation theory, as well as from non-perturbative techniques associated with certain characteristic features of specific theories. Among the topics of research were: the implications of abelian and non-abelian anomalies on the spectrum and possible dynamical symmetry breaking in any theory, topological and conformal properties of quantum fields in two and higher dimensions, the breaking of global chiral symmetries by vector-like gauge theories such as QCD, the phenomenological implications of a strongly interacting Higgs sector in the standard model, and the application of soliton ideas to the physics to be explored at the SSC.

  19. Theoretical and experimental investigation of optically spin-injected VECSEL (United States)

    Joly, Alexandre; Frougier, Julien; Baili, Ghaya; Alouini, Mehdi; George, Jean-Marie; Sagnes, Isabelle; Dolfi, Daniel


    We report theoretical and experimental analysis of spin-injected VECSELs. First, we fabricate and characterize an optically pumped (100)-oriented InGaAs/GaAsP multiple quantum well VECSEL. The structure is designed to allow the integration of a Metal-Tunnel-Junction ferromagnetic spin-injector for future electrical injection. We report here the control at room temperature of the VECSEL polarization using optical spin injection in the active medium. The switching between two highly circular polarization states had been demonstrated using an M-shaped extended cavity in multi-modes lasing. This first result witnesses an efficient spin-injection in the active medium of the laser. Then, we report birefringence measurements of the VECSEL in oscillating conditions. The proposed technique relies on the measurement in the microwave domain of the beatnote between the oscillating mode and the amplified spontaneous emission of the cross-polarized non-lasing field lying in the following longitudinal mode. This technique is shown to offer extremely high sensitivity and accuracy enabling to track the amount of residual birefringence according to the laser operation conditions. Finally, we discuss the compensation of the residual linear phase anisotropy by controlling the birefringence of an intracavity electro-optical crystal. A 44-fold birefringence reduction is obtained. Besides, we study the modification of the laser polarization eigen states with birefringence compensation: a rotation of the linear polarization state is observed when the total phase anisotropy is reduced. An elliptical polarization eigen state is obtained at the minimum of the birefringence into the laser cavity, more favorable for spin injection.

  20. Theoretical Investigations of Novel Materials for Nitrogen Fixation

    DEFF Research Database (Denmark)

    Howalt, Jakob Geelmuyden

    This thesis is dedicated to the investigation and design of new catalyst materials for electrochemical ammonia production and especially the properties of the under-coordinated reaction sites on nanoparticles has been studied in great detail. Additionally, a universal transition state relation go...

  1. Theoretical flow investigations of an all glass evacuated tubular collector

    DEFF Research Database (Denmark)

    Shah, Louise Jivan; Furbo, Simon


    the highest efficiency, the optimal inlet flow rate was around 0.4-1 kg/min, the flow structures in the glass tubes were relatively uninfluenced by the inlet flow rate, Generally, the results showed only small variations in the efficiencies. This indicates that the collector design is well working for most......Heat transfer and flow structures inside all glass evacuated tubular collectors for different operating conditions are investigated by means of computational fluid dynamics. The investigations are based on a collector design with horizontal tubes connected to a vertical 14 manifold channel. Three...... different tube lengths varying from 0.59 in to 1.47 in have been modelled with five different inlet mass flow rates varying from 0.05 kg/min to 10 kg/min with a constant inlet temperature of 333 K. Under these operating conditions the results showed that: the collector with the shortest tube length achieved...

  2. Theoretical investigation of the thermodynamic properties of metallic thin films

    Energy Technology Data Exchange (ETDEWEB)

    Hung, Vu Van [Vietnam Education Publishing House, 81 Tran Hung Dao, Hanoi (Viet Nam); Phuong, Duong Dai [Hanoi National University of Education, 136 Xuan Thuy, Hanoi (Viet Nam); Hoa, Nguyen Thi [University of Transport and Communications, Lang Thuong, Dong Da, Hanoi (Viet Nam); Hieu, Ho Khac, E-mail: [Institute of Research and Development, Duy Tan University, K7/25 Quang Trung, Danang (Viet Nam)


    The thermodynamic properties of metallic thin films with face-centered cubic structure at ambient conditions were investigated using the statistical moment method including the anharmonicity effects of thermal lattice vibrations. The analytical expressions of Helmholtz free energy, lattice parameter, linear thermal expansion coefficient, specific heats at the constant volume and constant pressure were derived in terms of the power moments of the atomic displacements. Numerical calculations of thermodynamic properties have been performed for Au and Al thin films and compared with those of bulk metals. This research proposes that thermodynamic quantities of thin films approach the values of bulk when the thickness of thin film is about 70 nm. - Highlights: • Thermodynamic properties of thin films were investigated using the moment method. • Expressions of Helmholtz energy, expansion coefficient, specific heats were derived. • Calculations for Au, Al thin films were performed and compared with those of bulks.

  3. Theoretical and experimental investigation of microstrip rhombic resonators (United States)

    Al-Charchafchi, S. H.; Boulkos, J.


    The resonant behavior of a novel microstrip rhombic resonator is investigated by analyzing an equivalent circuit based on transmission line modeling. Design curves showing the dependence of resonator performance on its parameters, as well as the substrate parameters, are presented. Experiments carried out showed a significant reduction in insertion loss when the rhombic resonator is dielectrically shielded. The resonator could be used as a microwave bandpass filter or a stabilization circuit for microwave oscillators in both hybrid and monolithic integrated circuits.

  4. Theoretical investigation of micropolar fluid flow between two porous disks

    Institute of Scientific and Technical Information of China (English)

    P Valipour; S E Ghasemi; M Vatani


    The steady, laminar, incompressible and two dimensional micropolar flow between two porous disks was investigated using optimal homotopy asymptotic method (OHAM) and fourth order Runge–Kutta numerical method. Comparison between OHAM and numerical method shows that OHAM is an exact and high efficient method for solving these kinds of problems. The results are presented to study the velocity and rotation profiles for different physical parameters such as Reynolds number, vortex viscosity parameter, spin gradient viscosity and microinertia density parameter. As an important outcome, the magnitude of the microrotation increases with an increase in the values of injection velocity while it decreases by increasing the values of suction velocity.

  5. Theoretical investigation on homoleptic Yttrium tri-guanidinates

    Directory of Open Access Journals (Sweden)

    Salima Lakehal


    Full Text Available The electronic and molecular structures of the homoleptic Yttrium tris-guanidinates complexes Y[(NiPr2CNR1R2]3, [R1 = R2 = Me, Et and iPr] have been investigated employing DFT calculations in order to understand the structures, bonding and energies of the interactions between Yttrium metal and guanidinate ligands. The effect of the substitution on nitrogen position of guanidinate in these complexes has been also investigated employing DFT and TDDFT calculations for six kinds of models obtained by alternative substitution of alkyl on nitrogen of the guanidinate ligands. The results reveal that the substitution position plays a crucial role in the geometric structure by affecting the torsion angle and the HOMO–LUMO transitions. The energy decomposition analysis indicates a majority of ionic bonding in all systems; the exception is in the M4 (Y[(NYR2CNCR1R2]3; R = Et and R1 = R2 = H which present a significant degree of covalency.

  6. Experimental and theoretical investigations into the stability of cyclic aminals

    Directory of Open Access Journals (Sweden)

    Edgar Sawatzky


    Full Text Available Background: Cyclic aminals are core features of natural products, drug molecules and important synthetic intermediates. Despite their relevance, systematic investigations into their stability towards hydrolysis depending on the pH value are lacking.Results: A set of cyclic aminals was synthesized and their stability quantified by kinetic measurements. Steric and electronic effects were investigated by choosing appropriate groups. Both molecular mechanics (MM and density functional theory (DFT based studies were applied to support and explain the results obtained. Rapid decomposition is observed in acidic aqueous media for all cyclic aminals which occurs as a reversible reaction. Electronic effects do not seem relevant with regard to stability, but the magnitude of the conformational energy of the ring system and pKa values of the N-3 nitrogen atom.Conclusion: Cyclic aminals are stable compounds when not exposed to acidic media and their stability is mainly dependent on the conformational energy of the ring system. Therefore, for the preparation and work-up of these valuable synthetic intermediates and natural products, appropriate conditions have to be chosen and for application as drug molecules their sensitivity towards hydrolysis has to be taken into account.

  7. A theoretical investigation of the (0001) covellite surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Gaspari, Roberto, E-mail: [D3-Computation, Istituto Italiano di Tecnologia, via Morego 30, Genova 16163 (Italy); Manna, Liberato [Department of Nanochemistry, Istituto Italiano di Tecnologia, via Morego 30, Genova 16163 (Italy); Cavalli, Andrea [D3-Computation, Istituto Italiano di Tecnologia, via Morego 30, Genova 16163 (Italy); Department of Pharmacy and Biotechnology, University of Bologna, via Belmeloro 6, I-40126 Bologna (Italy)


    We report on the properties of the (0001) covellites surfaces, which we investigate by periodic slab density functional theory calculations. The absolute surface energies have been computed for all bulk terminations, showing that surfaces terminated by the flat CuS layer are associated with the lowest surface energy. Cleavage is predicted to occur across the [0001] interlayer Cu–S bond. The surfaces obtained by lowest energy cleavage are analyzed in terms of the atomic vertical relaxation, workfunction, and surface band structure. Our study predicts the presence of a shallow p{sub z}-derived surface state located 0.26 eV below the Fermi level, which is set to play an important role in the surface reactivity of covellite.

  8. A theoretical investigation on the HCCS radical and its ions

    Energy Technology Data Exchange (ETDEWEB)

    Puzzarini, Cristina [Dipartimento di Chimica ' G. Ciamician' , Universita di Bologna, Via Selmi 2, I-40126 Bologna (Italy)], E-mail:


    The thioketenyl (HCCS) radical and its related cation, HCCS{sup +}, and anion, HCCS{sup -}, have been investigated at a high level of accuracy. The singles and doubles coupled-cluster method including a perturbational correction for connected triple excitations, CCSD(T), in conjunction with correlation consistent basis sets ranging in size from quadruple to sextuple zeta have been employed. Extrapolation to the complete basis set limit has been used with accurate treatments of core-valence correlation effects to accurately predict equilibrium structures, dipole moments as well as ionization potential and electron affinity. For all the species studied, harmonic vibrational frequencies have also been evaluated to obtain zero-point corrections to energies.

  9. Theoretical Investigation on Hyperfine Structures of Perfluoropolyether Radicals

    Institute of Scientific and Technical Information of China (English)

    DONG Su-li; LIU Ya-jun


    The geometries of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2 radicals were investigated by density func tional theory(DFT) method. The calculated results indicate that all the three radicals have pyramidal shapes at their centers, and the aC is one top of the pyramids. Based on the DFT optimized geometries, the hyperfine coupling con stants(hfcc's) of the 19F atoms of the three radicals were calculated by B3LYP, MP2(full) and QCISD(full) methods.The calculated values agree with the experimental values, especially for the a values of Fa, the a values are 125.6× 10-4, 104.2× 10-4, and 83.2× 10-4 T of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2, respectively. These results better explain the experimental observation.

  10. Theoretical Investigation on Triplet Excitation Energy Transfer in Fluorene Dimer

    Institute of Scientific and Technical Information of China (English)

    Yu-bing Si; Xin-xin Zhong; Wei-wei Zhang; Yi Zhao


    Triplet-triplet energy transfer in fluorene dimer is investigated by combining rate theories with electronic structure calculations.The two key parameters for the control of energy transfer,electronic conpling and reorganization energy,are calculated based on the diabatic states constructed by the constrained density functional theory.The fluctuation of the electronic coupling is further revealed by molecular dynamics simulation.Succeedingly,the diagonal and off-diagonal fluctuations of thc Hamiltonian are mapped from the correlation functions of those parameters,and the rate is then estimated both from the perturbation theory and wavepacket diffusion method.The results manifest that both the static and dynamic fluctuations enhance the rate significantly,but the rate from the dynamic fluctuation is smaller than that from the static fluctuation.

  11. Application of Ion Chromatography to the Investigation of Real-World Samples (United States)

    Whelan, Rebecca J.; Hannon, Theresa E.; Zare, Richard N.


    The use of ion chromatography (IC) as a means to teach important analytical concepts while giving the students a valuable opportunity to identify and investigate a real-world system of interest to them is described. A single IC apparatus can be tailored for different classes of analyses by the selection of different column-eluent combinations.

  12. Theoretical and Numerical Investigation of Radiative Extinction of Diffusion Flames (United States)

    Ray, Anjan


    The influence of soot radiation on diffusion flames was investigated using both analytical and numerical techniques. Soot generated in diffusion flames dominate the flame radiation over gaseous combustion products and can significantly lower the temperature of the flame. In low gravity situations there can be significant accumulation of soot and combustion products in the vicinity of the primary reaction zone owing to the absence of any convective buoyant flow. Such situations may result in substantial suppression of chemical activities in a flame, and the possibility of a radiative extinction may also be anticipated. The purpose of this work was to not only investigate the possibility of radiative extinction of a diffusion flame but also to qualitatively and quantitatively analyze the influence of soot radiation on a diffusion flame. In this study, first a hypothetical radiative loss profile of the form of a sech(sup 2) was assumed to influence a pure diffusion flame. It was observed that the reaction zone can, under certain circumstances, move through the radiative loss zone and locate itself on the fuel side of the loss zone contrary to our initial postulate. On increasing the intensity and/or width of the loss zone it was possible to extinguish the flame, and extinction plots were generated. In the presence of a convective flow, however, the movement of the temperature and reaction rate peaks indicated that the flame behavior is more complicated compared to a pure diffusional flame. A comprehensive model of soot formation, oxidation and radiation was used in a more involved analysis. The soot model of Syed, Stewart and Moss was used for soot nucleation and growth and the model of Nagle and Strickland-Constable was used for soot oxidation. The soot radiation was considered in the optically thin limit. An analysis of the flame structure revealed that the radiative loss term is countered both by the reaction term and the diffusion term. The essential balance for

  13. Theoretical investigation of second hyperpolarizability of trans-polyacetylene: Comparison between experimental and theoretical results for small oligomers (United States)

    Andrade, Ageo Meier de; Inacio, Patrícia Loren; Camilo, Alexandre


    The development of new conductive polymers nowadays is one of the most important technological areas in materials design. Computational investigation of desired properties in conductive polymers could save financial resources and time, but it is important to choose the methodology that produces good results comparing to experimental results. To verify the prediction of second hyperpolarizability (γ) in oligomers of Trans-Polyacetylene (TPA) by theoretical calculations, a series of semi-empirical, Hartree-Fock (HF), and Density Functional Theory (DFT) calculations were performed and analysed through linear fitting statistical analysis to investigate the accuracy of such theoretical predictions in comparison to the experimental ones. The results showed that HF and DFT methodologies do not describe γ with good accuracy, but the use of diffuse and polarizability functions in HF methodology provided better results than 3-21G and 6-31G functions. It was concluded that RM1 methodology better agrees with γ experimental results for TPA oligomers, and linear fitting statistical analysis is a useful tool to compare experimental and theoretical results.

  14. Theoretical and experimental investigation of shock wave stressing of metal powders by an explosion

    Directory of Open Access Journals (Sweden)

    Lukyanov Ya.L.


    Full Text Available Joint theoretical and experimental investigations have allowed to realize an approach with use of mathematical and physical modeling of processes of a shock wave loading of powder materials. Hugoniot adiabats of the investigated powder have been measured with a noncontact electromagnetic method. The mathematical model of elastic-plastic deformation of the powder media used in the investigation has been validated. Numerical simulation of shock wave propagation and experimental assembly deformation has been performed.

  15. Chromatography methods in investigation of lipophilicity of the biological active substances

    Directory of Open Access Journals (Sweden)

    Odović Jadranka V.


    Full Text Available This paper presents the review of the methods used in research of the biological active substances hydrophobicity, a very important property. The biological activity of some substances depends on their pharmacokinetics and pharmacodynamics. These processes depend on the molecule's capability to interact with two different media: aqueous (cells interior and non-aqueous (cells membrane, or on the molecule lipophilicity. Today, great attention is given to investigation and systematic determination of drugs lipophilicity. In these researches chromatography methods have an important role.

  16. Experimental and theoretical investigation of high gradient acceleration. Progress report, June 1, 1991--February 1, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Bekefi, G.; Chen, C.; Chen, S.; Danly, B.; Temkin, R.J.; Wurtele, J.S.


    This report contains a technical progress summary of the research conducted under the auspices of DOE Grant No. DE-FG0291ER-40648. ``Experimental and Theoretical Investigations of High Gradient Acceleration.`` This grant supports three research tasks: Task A consists of the design and fabrication of a 17GHz of photocathode gun, Task B supports the testing of high gradient acceleration using a 33GHz structure, and Task C comprises theoretical investigations, both in support of the experimental tasks and on critical physics issues for the development of high energy linear colliders. This report is organized as follows. The development of an rf gun design and research progress on the picosecond laser system is summarized in Sec. 2, the status of the studies of the LBL/Haimson high gradient structure, using a 50 MW free-electron laser is summarized in Sec. 3, and theoretical research progress is described in Sec. 4. Supporting material is contained in Appendices A-G.

  17. Experimental and Theoretical Investigation of Subnanosecond Pulse Propagation in Graded Index Fibers

    DEFF Research Database (Denmark)

    Nicolaisen, Ejner; Hansen, J. J. Ramskov


    The propagation in a fibre which does not exhibit any mode coupling is investigated by varying the launching conditions. It is shown that for this fibre there exists a trade-off between dispersion and power coupling efficiency. The measurements are compared to theoretical calculations taking leak...

  18. Theoretical investigation of the hyperfine structure in spatially and spin degenerate electronic states

    Directory of Open Access Journals (Sweden)



    Full Text Available The present paper reviews the results of ab initio studies on the magnetic hyperfine structure in spectra of spatially and spin degenerate electronic states of triatomic and tetra-atomic molecules. The main goal of the present paper is to show that such theoretical investigations can be used to reliably reproduce, explain and predict the results of the corresponding measurements.

  19. Comparative experimental and theoretical investigations of the DM neutron moisture probe

    DEFF Research Database (Denmark)

    Ølgaard, Povl Lebeck; Haahr, Vagner


    Theoretical and experimental investigations of the Danish produced DM subsurface moisture probe have been carried out at the Research Establishment Risö, and the results obtained are presented in this paper. The DM probe contains an Am-Be fast neutron source and has a glass scintillator containi...

  20. Theoretical investigation of van der Waals forces between solid surfaces at nanoscales

    NARCIS (Netherlands)

    Kudryavtsev, Y.V.; Gelinck, E.R.M.; Fischer, H.R.


    A theoretical investigation of van der Waals forces acting between two solid silicon surfaces at separations from zero to approximately 20 nm is presented. We focused our efforts on the analysis of different factors that can cause deviations from the classical pressure-distance dependence p ∼ 1/D3.

  1. Theoretical and experimental investigation into the influence factors for range gated reconstruction (United States)

    Chua, Sing Yee; Wang, Xin; Guo, Ningqun; Tan, Ching Seong


    Range gated is a laser ranging technique that has been applied in various fields due to its good application prospects. In order to improve the effectiveness of this method, influence factors contributing to the system performance should be well understood. Thus this paper performs theoretical and experimental investigation to comprehend the effects caused by multiple factors on range gated reconstruction. Our study focuses on the distance, target reflection, and acquisition time step parameter where their impacts on the quality of range reconstruction are analyzed. The presented experimental results show the expected trends of range error to support the validity of our theoretical model and discussion which can be used in future improvement works.

  2. Theoretical and Experimental Investigation of Ultrasonic Focusing with Annular Phased Array

    Institute of Scientific and Technical Information of China (English)

    ZHANG Bi-Xing; WANG Cheng-Hao; LAI Pu-Xiang


    @@ The focused acoustic field generated by an annular array transducer and its reflection field on a solid-liquid interface are investigated theoretically and experimentally. Theoretically, the concise analytic expressions about the radiation and reflection acoustic fields of the annular phased array are obtained by the ray approach method (saddle-point method). In experiment, an annular transducer with 8 equal-area elements is designed and fabricated, and a series of experiments about the radiation acoustic field and its reflection on the liquid-solid interface are carried out. The experimental characteristics of the transducer are in good agreement with the numerical ones. It shows the correctness of the theoretical result and the feasibility of dynamic focusing of the experiment system. With the maximum amplitude and its emergence time of the reflection wave, we can acquire the information and the imaging of the reflection interface by the annular phased array dynamic focusing.

  3. Miniaturized ultra-high performance liquid chromatography coupled to electrochemical detection: Investigation of system performance for neurochemical analysis. (United States)

    Van Schoors, Jolien; Maes, Katrien; Van Wanseele, Yannick; Broeckhoven, Ken; Van Eeckhaut, Ann


    The interest in implementation of miniaturized ultra-high performance liquid chromatography (UHPLC) in neurochemical research is growing because of the need for faster, more selective and more sensitive neurotransmitter analyses. The instrument performance of a tailor designed microbore UHPLC system coupled to electrochemical detection (ECD) is investigated, focusing on the quantitative monoamine determination in in vivo microdialysis samples. The use of a microbore column (1.0mm I.D.) requires miniaturization of the entire instrument, though a balance between extra-column band broadening and injection volume must be considered. This is accomplished through the user defined Performance Optimizing Injection Sequence, whereby 5 μL sample is injected on the column with a measured extra-column variance of 4.5-9.0 μL(2) and only 7 μL sample uptake. Different sub-2 μm and superficially porous particle stationary phases are compared by means of the kinetic plot approach. Peak efficiencies of about 16000-35000 theoretical plates are obtained for the Acquity UPLC BEH C18 column within 13 min analysis time. Furthermore, the coupling to ECD is shown suitable for microbore UHPLC analysis thanks to the miniaturized flow cell design, sufficiently fast data acquisition and mathematical data filtering. Ultimately, injection of in vivo samples demonstrates the applicability of the system for microdialysis analysis.

  4. Multi-scale theoretical investigation of hydrogen storage in covalent organic frameworks. (United States)

    Tylianakis, Emmanuel; Klontzas, Emmanouel; Froudakis, George E


    The quest for efficient hydrogen storage materials has been the limiting step towards the commercialization of hydrogen as an energy carrier and has attracted a lot of attention from the scientific community. Sophisticated multi-scale theoretical techniques have been considered as a valuable tool for the prediction of materials storage properties. Such techniques have also been used for the investigation of hydrogen storage in a novel category of porous materials known as Covalent Organic Frameworks (COFs). These framework materials are consisted of light elements and are characterized by exceptional physicochemical properties such as large surface areas and pore volumes. Combinations of ab initio, Molecular Dynamics (MD) and Grand Canonical Monte-Carlo (GCMC) calculations have been performed to investigate the hydrogen adsorption in these ultra-light materials. The purpose of the present review is to summarize the theoretical hydrogen storage studies that have been published after the discovery of COFs. Experimental and theoretical studies have proven that COFs have comparable or better hydrogen storage abilities than other competitive materials such as MOF. The key factors that can lead to the improvement of the hydrogen storage properties of COFs are highlighted, accompanied with some recently presented theoretical multi-scale studies concerning these factors.

  5. Preliminary phytochemical investigation and thin layer chromatography profiling of sequential extracts of Moringa oleifera pods

    Directory of Open Access Journals (Sweden)

    Veena Sharma


    Full Text Available Context: Moringa oleifera Lam (Moringaceae is a highly valued plant, distributed in many countries of the tropics and subtropics. It has an impressive range of medicinal uses with high nutritional value. Aim: The present study, primarily aims to carry out a preliminary phytochemical screening so as to detect the major class of compounds present in M. oleifera and to perform thin layer chromatography (TLC profiling of all sequential extracts. Materials and Methods: Phytochemical analysis was performed by various qualitative methods and TLC profiling was carried out using various solvent system of varying polarity. Results and Conclusions: Qualitative phytochemical analysis reflects the presence of phenolics, triterpenoids, cardiac glycosides, steroid, alkaloids and saponin in the plant extract. TLC profiling of the M. oleifera pods was carried out using sequential extracts of petroleum ether, benzene, petroleum ether, benzene, chloroform, ethyl acetate, ethanol and water respectively. The results obtained in the present investigation indicated M. oleifera pods as a rich source of natural antioxidants.

  6. Mass and position determination in MEMS mass sensors: a theoretical and an experimental investigation (United States)

    Bouchaala, Adam; Nayfeh, Ali H.; Jaber, Nizar; Younis, Mohammad I.


    We present a method to determine accurately the position and mass of an entity attached to the surface of an electrostatically actuated clamped-clamped microbeam implemented as a mass sensor. In the theoretical investigation, the microbeam is modeled as a nonlinear Euler-Bernoulli beam and a perturbation technique is used to develop a closed-form expression for the frequency shift due to an added mass at a specific location on the microbeam surface. The experimental investigation was conducted on a microbeam made of Polyimide with a special lower electrode to excite both of the first and second modes of vibration. Using an ink-jet printer, we deposited droplets of polymers with a defined mass and position on the surface of the microbeam and we measured the shifts in its resonance frequencies. The theoretical predictions of the mass and position of the deposited droplets match well with the experimental measurements.

  7. Theoretical Investigation of Subwavelength Gratings and Vertical Cavity Lasers Employing Grating Structures

    DEFF Research Database (Denmark)

    Taghizadeh, Alireza

    This thesis deals with theoretical investigations of a newly proposed grating structure, referred to as hybrid grating (HG) as well as vertical cavity lasers based on the grating reflectors. The HG consists of a near-subwavelength grating layer and an unpatterned high-refractive-index cap layer...... behind these reflector and resonator properties are studied thoroughly. A HG structure comprising a III-V cap layer with a gain material and a Si grating layer enables the realization of a compact vertical cavity laser integrated on Si platform, which has a superior thermal property and fabrication...... directions, which is analogous to electronic quantum wells in conduction or valence bands. Several interesting configurations of heterostructures have been investigated and their potential in fundamental physics study and applications are discussed. For numerical and theoretical studies, a three...

  8. Mass and position determination in MEMS mass sensors: a theoretical and an experimental investigation

    KAUST Repository

    Bouchaala, Adam M.


    We present a method to determine accurately the position and mass of an entity attached to the surface of an electrostatically actuated clamped-clamped microbeam implemented as a mass sensor. In the theoretical investigation, the microbeam is modeled as a nonlinear Euler-Bernoulli beam and a perturbation technique is used to develop a closed-form expression for the frequency shift due to an added mass at a specific location on the microbeam surface. The experimental investigation was conducted on a microbeam made of Polyimide with a special lower electrode to excite both of the first and second modes of vibration. Using an ink-jet printer, we deposited droplets of polymers with a defined mass and position on the surface of the microbeam and we measured the shifts in its resonance frequencies. The theoretical predictions of the mass and position of the deposited droplets match well with the experimental measurements.

  9. The physics and chemistry of dusty plasmas: A laboratory and theoretical investigation (United States)

    Whipple, E. C.


    Theoretical work on dusty plasmas was conducted in three areas: collective effects in a dusty plasma, the role of dusty plasmas in cometary atmospheres, and the role of dusty plasmas in planetary atmospheres (particularly in the ring systems of the giant planets). Laboratory investigations consisted of studies of dust/plasma interactions and stimulated molecular excitation and infrared emission by charged dust grains. Also included is a list of current publications.

  10. Theoretical study of closed-loop recycling liquid-liquid chromatography and experimental verification of the theory. (United States)

    Kostanyan, Artak E; Erastov, Andrey A


    The non-ideal recycling equilibrium-cell model including the effects of extra-column dispersion is used to simulate and analyze closed-loop recycling counter-current chromatography (CLR CCC). Previously, the operating scheme with the detector located before the column was considered. In this study, analysis of the process is carried out for a more realistic and practical scheme with the detector located immediately after the column. Peak equation for individual cycles and equations describing the transport of single peaks and complex chromatograms inside the recycling closed-loop, as well as equations for the resolution between single solute peaks of the neighboring cycles, for the resolution of peaks in the recycling chromatogram and for the resolution between the chromatograms of the neighboring cycles are presented. It is shown that, unlike conventional chromatography, increasing of the extra-column volume (the recycling line length) may allow a better separation of the components in CLR chromatography. For the experimental verification of the theory, aspirin, caffeine, coumarin and the solvent system hexane/ethyl acetate/ethanol/water (1:1:1:1) were used. Comparison of experimental and simulated processes of recycling and distribution of the solutes in the closed-loop demonstrated a good agreement between theory and experiment.

  11. Theoretical investigation on peripheral ligands of oxygen-evolving center in photosystem II

    Institute of Scientific and Technical Information of China (English)


    The interaction between the Mn-cluster and its peripheral ligands in oxygen-evolving center is still unclear. Theoretical investigation on the coordination of histidine, H2O, and Cl to Mn2O2 units in OEC is conducted. The following conclusions are obtained: (i) both histidine and H2O molecule, bound to the two Mn ions, respectively, are vertical to the Mn2O2 plane, and maintain a large distance; (ii) the two H2O molecules cannot bind to the same Mn2O2 unit. Based on Mn-cluster structure in OEC, we theoretically predict that two H2O molecules bind to the two Mn ions at the "C"-shaped open end in S0 state, while two His residues at the closed end. Cl ion can only terminally ligate at the open end. Individual valence for the four Mn ions in S0 state is assigned.

  12. Investigating the Retention Mechanisms of Liquid Chromatography Using Solid-Phase Extraction Cartridges (United States)

    O'Donnell, Mary E.; Musial, Beata A.; Bretz, Stacey Lowery; Danielson, Neil D.; Ca, Diep


    Liquid chromatography (LC) experiments for the undergraduate analytical laboratory course often illustrate the application of reversed-phase LC to solve a separation problem, but rarely compare LC retention mechanisms. In addition, a high-performance liquid chromatography instrument may be beyond what some small colleges can purchase. Solid-phase…

  13. Theoretical and experimental investigation of aqueous liquids contained in carbon nanotubes (United States)

    Yarin, Alexander L.; Yazicioglu, Almila G.; Megaridis, Constantine M.; Rossi, Maria Pia; Gogotsi, Yury


    The dynamic response—as caused by different means of thermal stimulation or pressurization—of aqueous liquid attoliter volumes contained inside carbon nanotubes is investigated theoretically and experimentally. The experiments indicate an energetically driven mechanism responsible for the dynamic multiphase fluid behavior visualized in real time with high spatial resolution using electron microscopy. The theoretical model is formulated using a continuum approach, which combines temperature-dependent mass diffusion with intermolecular interactions in the fluid bulk, as well as in the vicinity of the carbon walls. Intermolecular forces are modeled by Lennard-Jones potentials. Several one-dimensional and axisymmetric cases are considered. These include situations which physically represent liquid volume pinchoff, jetting, or fluid relocation due to thermal stimulation by a steady or modulated electron beam, as well as liquid precipitation (condensation) from vapor due to overcooling or pressurization. Comparisons between theoretical predictions and experimental data demonstrate the ability of the model to describe the characteristic trends observed in the experiments.

  14. Theoretical investigation of frequency characteristics of free oscillation and injection-locked magnetrons (United States)

    Yue, Song; Gao, Dong-ping; Zhang, Zhao-chuan; Wang, Wei-long


    The frequency characteristics of free oscillation magnetron (FOM) and injection-locked magnetron (ILM) are theoretically investigated. By using the equal power voltage obtained from the experiment data, expressions of the frequency and radio frequency (RF) voltage of FOM and ILM, as well as the locking bandwidth, on the anode voltage and magnetic field are derived. With the increase of the anode voltage and the decrease of the magnetic field, the power and its growth rate increase, while the frequency increases and its growth rate decreases. The theoretical frequency and power of FOM agree with the particle-in-cell (PIC) simulation results. Besides, the theoretical trends of the power and frequency with the anode voltage and magnetic field are consistent with the experimental results, which verifies the accuracy of the theory. The theory provides a novel calculation method of frequency characteristics. It can approximately analyze the power and frequency of both FOM and ILM, which promotes the industrial applications of magnetron and microwave energy. Project supported by the National Basic Research Program of China (Grant No. 2013CB328901) and the National Natural Science Foundation of China (Grant No. 11305177).

  15. Synthesis, characterization, investigation of biological activity and theoretical studies of hydrazone compounds containing choloroacetyl group (United States)

    Cukurovali, Alaaddin; Yilmaz, Engin


    In this study, three new hydrazide-hydrazone derivative compounds which contain choloroacetyl group have been synthesized and characterized. In the characterization, spectral techniques such as IR, 1H NMR, 13C NMR and UV-Vis spectroscopy techniques were used. Antibacterial effects of the synthesized compounds were investigated against Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853. In the theoretical calculations Gaussian 09 software was used with the DFT/6-311+(d,p) basis set. Experimental X-ray analysis of compounds has not been studied. Theoretical bond lengths of synthesized compounds were compared with experimental bond lengths of a similar compound. Theoretical and experimental bond lengths are in good agreement with R2: 0.896, 0.899 and 0.900 for compounds 1, 2, and 3, respectively. For antibacterial activity, the most effective one was found to be N‧-(4-bromobenzylidene)-2-chloro-N-(4-(3-methyl-3-phenylcyclobutyl)-thiazol-2-yl) acetohydrazide against P.aeroginaosa ATTC 27853, among the studied compounds.

  16. An Experimental and Theoretical Investigation of Micropiiting in Wind Turbine Gears and Bearings

    Energy Technology Data Exchange (ETDEWEB)

    Kahraman, Ahmet


    In this research study, the micro-pitting related contact failures of wind turbine gearbox components were investigated both experimentally and theoretically. On the experimental side, a twin-disk type test machine was used to simulate wind turbine transmission contacts in terms of their kinematic (rolling and sliding speeds), surface roughnesses, material parameters and lubricant conditions. A test matrix that represents the ranges of contact conditions of the wind turbine gear boxes was defined and executed to bring an empirical understanding to the micro-pitting problem in terms of key contact parameters and operating conditions. On the theoretical side, the first deterministic micro-pitting model based on a mixed elastohydrodynamic lubrication formulations and multi-axial near-surface crack initiation model was developed. This physics-based model includes actual instantaneous asperity contacts associated with real surface roughness profiles for predicting the onset of the micro-pit formation. The predictions from the theoretical model were compared to the experimental data for validation of the models. The close agreement between the model and measurements was demonstrated. With this, the proposed model can be deemed suitable for identifying the mechanisms leading to micro-pitting of gear and bearing surfaces of wind turbine gear boxes, including all key material, lubricant and surface engineering aspects of the problem, and providing solutions to these micro-pitting problems.

  17. Experimental and Theoretical Investigation of Valence Orbitals in 1,4-Dioxane by Electron momentum Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    YANG Tie-Cheng; NING Chuan-Gang; SU Guo-Lin; DENG Jing-Kang; ZHANG Shu-Feng; REN Xue-Guang; HUANG Yan-Ru


    @@ The binding energy spectrum of all valence orbitals and the momentum distributions of highest occupied molecular orbital (HOMO: 8ag), 7bu + 7ag, 4bu, 2bg + 4ag and 2au in 1, 4-dioxane are investigated by electron momentum spectroscopy (EMS) with 600 e V impact energy. The experimental results are consistent with theoretical calculations of C2h chair conformation using the Hartree-Fock method and density functional theory with 6-311++G**and A UG-CC-PVTZ basis sets.

  18. Strain-free polarization superlattice in silicon carbide: a theoretical investigation. (United States)

    Deák, Peter; Buruzs, Adam; Gali, Adam; Frauenheim, Thomas


    A strain-free superlattice of inversion domains along the hexagonal axis of SiC is investigated by theoretical calculations. The induced polarization causes a zigzag shape in the band edges, leading to spatial separation of photoexcited carriers and to an effective band gap narrowing tunable over a wide range by the geometry and on a smaller scale by the intensity of the excitation. Calculations on the SiC surface indicate that preparation of such a superlattice might be possible in atomic layer epitaxy with properly chosen sources and temperatures.

  19. Theoretical investigation on a general class of 2D quasicrystals with the rectangular projection method (United States)

    Yue, Yang-Yang; Lu, Rong-er; Yang, Bo; Huang, Huang; Hong, Xu-Hao; Zhang, Chao; Qin, Yi-Qiang; Zhu, Yong-Yuan


    We take a theoretical investigation on the reciprocal property of a class of 2D nonlinear photonic quasicrystal proposed by Lifshitz et al. in PRL 95, 133901 (2005). Using the rectangular projection method, the analytical expression for the Fourier spectrum of the quasicrystal structure is obtained explicitly. It is interesting to find that the result has a similar form to the corresponding expression of the well-known 1D Fibonacci lattice. In addition, we predict a further extension of the result to higher dimensions. This work is of practical importance for the photonic device design in nonlinear optical conversion progresses.

  20. Experimental and theoretical investigation of timing jitter inside a stretcher-compressor setup. (United States)

    Klingebiel, Sandro; Ahmad, Izhar; Wandt, Christoph; Skrobol, Christoph; Trushin, Sergei A; Major, Zsuzsanna; Krausz, Ferenc; Karsch, Stefan


    In an optically synchronized short-pulse optical-parametric chirped-pulse amplification (OPCPA) system, we observe a few-100 fs-scale timing jitter. With an active timing stabilization system slow fluctuations are removed and the timing jitter can be reduced to 100 fs standard deviation (Std). As the main source for the timing fluctuations we could identify air turbulence in the stretcher-compressor setup inside the chirped pulse amplification (CPA) pump chain. This observation is supported by theoretical investigation of group delay changes for angular deviations occurring between the parallel gratings of a compressor or stretcher, as they can be introduced by air turbulence.

  1. Theoretical and experimental investigation of photophysical properties of Zn(DFP SAMQ)2 (United States)

    Valiev, R. R.; Telminov, E. N.; Solodova, T. A.; Ponyavina, E. N.; Gadirov, R. M.; Kaplunov, M. G.; Kopylova, T. N.


    Theoretical calculations and experimental measurements were carried out for the investigation of spectroscopic and photophysical properties of Zn(DFP SAMQ)2 complex. The rate constant of intersystem crossing and the radiative rate constant were calculated using ab initio method. The rate constant of the internal conversion was estimated using the received calculated values and the experimental fluorescence quantum yield. It was shown that the main mechanism for the deactivation of the excited electronic energy of the first singlet excited state is the process of internal conversion.

  2. Experimental and theoretical investigations on the antioxidant activity of isoorientin from Crotalaria globosa (United States)

    Deepha, V.; Praveena, R.; Sivakumar, Raman; Sadasivam, K.


    The increasing interests in naturally occurring flavonoids are well known for their bioactivity as antioxidants. The present investigations with combined experimental and theoretical methods are employed to determine the radical scavenging activity and phytochemicals present in Crotalaria globosa, a novel plant source. Preliminary quantification of ethanolic extract of leaves shows high phenolic and flavonoid content than root extract; also it is validated through DPPHrad assay. Further analysis is carried out with successive extracts of leaves of varying polarity of solvents. In DPPHrad and FRAP assays, ethyl acetate fraction (EtOAc) exhibit higher scavenging activity followed by ethanol fraction (EtOH) whereas in NOS assay ethanol fraction is slightly predominant over the EtOAc fraction. The LC-MS analysis provides tentative information about the presence of flavonoid C-glycoside in EtOAc fraction (yellow solid). Presence of flavonoid isorientin has been confirmed through isolation (PTLC) and detected by spectroscopy methods (UV-visible and 1H NMR). Utilizing B3LYP/6-311G (d,p) level of theory the structure and reactivity of flavonoid isoorientin theoretically have been explored. The analysis of the theoretical Bond dissociation energy values, for all Osbnd H sites of isoorientin reveals that minimum energy is required to dissociate H-atom from B-ring than A and C-rings. In order to validate the antioxidant characteristics of isoorientin the relevant molecular descriptors IP, HOMO-LUMO, Mulliken spin density analysis and molecular electrostatic potential surfaces have been computed and interpreted. From experimental and theoretical results, it is proved that isoorientin can act as potent antiradical scavenger in oxidative system.

  3. Measurements of association constants between enantiomers and chiral selectors by capillary gas chromatography. Theoretical and practical considerations. (United States)

    Lebed, Pablo J; Keunchkarian, Sonia; Osorio Grisales, Jaiver; Castells, Cecilia B


    The association constants of several volatile enantiomers with octakis(3-O-butanoyl-2,6-di-O-pentyl)-γ-cyclodextrin at temperatures between 50 and 100 °C were measured by gas-liquid chromatography using capillary columns coated with different amounts of chiral selector dissolved in polysiloxane OV-1701 and prepared with a precisely determined phase ratio. Simple expressions were deduced to estimate the apparent distribution constants from accurate hold-up and retention times along with that known phase ratio at each temperature. The enantiomer-chiral selector association constants were then calculated from the linear regression of the apparent constants as a function of the chiral selector concentration. One aim of this study consisted in discussing all the experimental uncertainties inherent in the determination of enantiomer/selector association constants with chiral analytes, and how these fundamental measurements can be performed precisely without resorting to the use of reference solutes.

  4. Intramolecular Hydrogen Bonding Involving Organic Fluorine: NMR Investigations Corroborated by DFT-Based Theoretical Calculations

    Directory of Open Access Journals (Sweden)

    Sandeep Kumar Mishra


    Full Text Available The combined utility of many one and two dimensional NMR methodologies and DFT-based theoretical calculations have been exploited to detect the intramolecular hydrogen bond (HB in number of different organic fluorine-containing derivatives of molecules, viz. benzanilides, hydrazides, imides, benzamides, and diphenyloxamides. The existence of two and three centered hydrogen bonds has been convincingly established in the investigated molecules. The NMR spectral parameters, viz., coupling mediated through hydrogen bond, one-bond NH scalar couplings, physical parameter dependent variation of chemical shifts of NH protons have paved the way for understanding the presence of hydrogen bond involving organic fluorine in all the investigated molecules. The experimental NMR findings are further corroborated by DFT-based theoretical calculations including NCI, QTAIM, MD simulations and NBO analysis. The monitoring of H/D exchange with NMR spectroscopy established the effect of intramolecular HB and the influence of electronegativity of various substituents on the chemical kinetics in the number of organic building blocks. The utility of DQ-SQ technique in determining the information about HB in various fluorine substituted molecules has been convincingly established.

  5. A Comprehensive Theoretical Investigation of the Molecular Properties of Methyl Bromide (CH3Br) (United States)

    Yu, Ang-Yang; Efil, Kürşat; Yang, Rui; Hu, Qing-Miao


    The properties of the ground and the lowest excited state of methyl bromide (CH3Br) have been studied with and without inclusion of the solvent effects in this work. The geometric parameters, energies, and frequencies of the ground state and the triplet state are calculated by using the MP2(full)/6-311++G** level of theory. The vertical excitation for the singlet state is also investigated. It is found that the theoretical results performed by the TDDFT/B3P86/6-311++G** method are in the best agreement with the experimental results. In addition, the dissociation energy of CH3Br molecule is computed at MP2(full)/6-311++G** level of theory for the gas phase and in water. The ionisation potential (IP), electron affinity (EA), electronegativity (χ), electrophilicity index (ω), hardness (η), softness (S), and chemical potential (μ) values are calculated from HOMO-LUMO energies both in the gas phase and in solvent (water). These theoretical results could serve as a guide for future experimental investigations.

  6. Theoretical investigations on model ternary polypeptides using genetic algorithm—Some new results (United States)

    Arora, Vinita; Bakhshi, A. K.


    Using genetic algorithm (GA) model ternary polypeptides containing glycine, alanine and serine in β-pleated conformation have been theoretically investigated. In designing, the criterion to attain the optimum solution at the end of GA run is minimum band gap and maximum delocalization in the polypeptide chain. Ab initio results obtained using Clementi's minimal basis set are used as input. Effects of (i) change of basis set from minimal to double zeta, (ii) change in secondary structure from β-pleated to α-helical, (iii) presence of solvation shell and (iv) binding of H + and Li + ions to peptide group on the resulting solution as well as on electronic structure and conduction properties of polypeptides are investigated. A comparison is drawn between results obtained for the two cationic adducts. The protonated adduct is expected to withdraw more negative charge from the polypeptide chain due to smaller size of H + and is found to have high electron affinity compared to Li + adduct.

  7. Experimental and theoretical investigation of the magnetization dynamics of an artificial square spin ice cluster (United States)

    Pohlit, Merlin; Stockem, Irina; Porrati, Fabrizio; Huth, Michael; Schröder, Christian; Müller, Jens


    We study the magnetization dynamics of a spin ice cluster which is a building block of an artificial square spin ice fabricated by focused electron-beam-induced deposition both experimentally and theoretically. The spin ice cluster is composed of twelve interacting Co nanoislands grown directly on top of a high-resolution micro-Hall sensor. By employing micromagnetic simulations and a macrospin model, we calculate the magnetization and the experimentally investigated stray field emanating from a single nanoisland. The parameters determined from a comparison with the experimental hysteresis loop are used to derive an effective single-dipole macrospin model that allows us to investigate the dynamics of the spin ice cluster. Our model reproduces the experimentally observed non-deterministic sequences in the magnetization curves as well as the distinct temperature dependence of the hysteresis loop.

  8. Theoretical and Experimental Investigation of Force Estimation Errors Using Active Magnetic Bearings with Embedded Hall Sensors

    DEFF Research Database (Denmark)

    Voigt, Andreas Jauernik; Santos, Ilmar


    This paper gives an original theoretical and experimental contribution to the issue of reducing force estimation errors, which arise when applying Active Magnetic Bearings (AMBs) with pole embedded Hall sensors for force quantification purposes. Motivated by the prospect of increasing the usability...... of AMBs by embedding Hall sensors instead of mounting these directly on the pole surfaces, force estimation errors are investigated both numerically and experimentally. A linearized version of the conventionally applied quadratic correspondence between measured Hall voltage and applied AMB force...... for pole embedded and pole surface mounted Hall sensors. It is shown that in a given range of bias currents and rotor offsets, pole embedded and surface mounted Hall sensors perform equally well for the four pole heteropolar flux-split radial AMB under investigation. Furthermore, frequency dependence...

  9. Experimental and theoretical investigation on high-Tc superconducting intrinsic Josephson junctions (United States)

    Grib, Alexander; Shukrinov, Yury; Schmidl, Frank; Seidel, Paul


    Within the last years many groups have realized and investigated different types of intrinsic Josephson junction (IJJ) arrays out of high-temperature superconducting single crystals or thin films. We tried to improve the synchronization between the junctions by external shunts. Mesa structures as well as microbridges on vicinal cut substrates showed multi-branch behaviour in their IV characteristics and random switching between branches. Theoretical modelling was done investigating phase dynamics and stability numerically as well as analytically. Branch structure in current voltage characteristics of IJJ is studied in the framework of different models, particularly, in capacitevely coupled Josephson junctions (CCJJ) model and CCJJ model with diffusion current. Results of modelling of return current in IV characteristics for stacks with different number of IJJ are presented. We discussed the possible mechanisms of synchronization and the ranges of stability. Conclusions with respect to application of such arrays such as radiation sources were given.

  10. Thin-Layer Chromatography/Desorption Electrospray Ionization Mass Spectrometry: Investigation of Goldenseal Alkaloids

    Energy Technology Data Exchange (ETDEWEB)

    Van Berkel, Gary J [ORNL; Tomkins, Bruce A [ORNL; Kertesz, Vilmos [ORNL


    Desorption electrospray ionization mass spectrometry was investigated as a means to qualitatively identify and to quantify analytes directly from developed normal-phase thin layer chromatography plates. The atmospheric sampling capillary of a commercial ion trap mass spectrometer was extended to permit sampling and ionization of analytes in bands separated on intact TLC plates (up to 10 cm x 10 cm). A surface positioning software package and the appropriate hardware enabled computer-controlled surface scanning along the length of development lanes or at fixed RF value across the plates versus the stationary desorption electrospray emitter. Goldenseal (Hydrastis canadensis) and related alkaloids and commercial dietary supplements were used as standards and samples. Alkaloid standards and samples were spotted and separated on aluminum- or glass-backed plates using established literature methods. The mass spectral signal levels as a function of desorption spray solvent were investigated with acetonitrile proving superior to methanol. The detection levels (ca. 5 ng each or 14 -28 pmol) in mass spectral full scan mode were determined statistically from the calibration curves (2.5 - 100 pmol) for the standards berberine, palmatine and hydrastinine spotted as a mixture and separated on the plates. Qualitative screening of the major alkaloids present in six different over-the-counter "goldenseal" dietary supplements was accomplished by obtaining full scan mass spectra during surface scans along the development lane in the direction of increasing RF value. In one sample, alkaloids were detected that strongly suggested the presence of at least one additional herb undeclared on the product label. These same data indicated the misidentification of one of the alkaloids in the TLC literature. Quantities of the alkaloids present in two of the samples determined using the mass spectral data were in reasonable agreement with the label values indicating the quantitative ability of

  11. Theoretical investigations on model ternary polypeptides using genetic algorithm-Some new results

    Energy Technology Data Exchange (ETDEWEB)

    Arora, Vinita [Department of Chemistry, University of Delhi, Delhi 110 007 (India); Bakhshi, A.K., E-mail: [Department of Chemistry, University of Delhi, Delhi 110 007 (India)


    Graphical abstract: Model ternary polypeptide chains consisting of glycine, alanine and serine amino acids as repeat units in anti-parallel {beta}-pleated sheet conformation have been theoretically investigated and designed using the genetic algorithm. The optimum solution or the polypeptide chain being searched for using the algorithm is the one having minimum band gap and maximum electronic delocalization in the polypeptide chain. The effects of (i) change of basis set from minimal to double zeta, (ii) change in secondary structure from {beta}-pleated to {alpha}-helical, (iii) presence of solvation shell, and (iv) binding of ions such as H{sup +} and Li{sup +} to the peptide group on the resulting optimum solution as well as on electronic structure and conduction properties of polypeptides have been investigated taking the ab initio Hartree-Fock crystal orbital results as input. The band gap value was also found to decrease in presence of a solvation shell, in presence of cations in the vicinity of the polypeptide chain as well as with the use of an improved basis set. Highlights: {yields} GA has been used for theoretical tailoring of aperiodic ternary polypeptides. {yields} Band gap of polypeptide chain decreases in presence of solvation shell. {yields} Band gap decreases in presence of cations in the vicinity of the chain. {yields} H{sup +} ion acts as a strong electron acceptor than Li{sup +} ion due to smaller size. - Abstract: Using genetic algorithm (GA) model ternary polypeptides containing glycine, alanine and serine in {beta}-pleated conformation have been theoretically investigated. In designing, the criterion to attain the optimum solution at the end of GA run is minimum band gap and maximum delocalization in the polypeptide chain. Ab initio results obtained using Clementi's minimal basis set are used as input. Effects of (i) change of basis set from minimal to double zeta, (ii) change in secondary structure from {beta}-pleated to {alpha

  12. Nonlinear dynamics of an electrically actuated mems device: Experimental and theoretical investigation

    KAUST Repository

    Ruzziconi, Laura


    This study deals with an experimental and theoretical investigation of an electrically actuated micro-electromechanical system (MEMS). The experimental nonlinear dynamics are explored via frequency sweeps in a neighborhood of the first symmetric natural frequency, at increasing values of electrodynamic excitation. Both the non-resonant branch, the resonant one, the jump between them, and the presence of a range of inevitable escape (dynamic pull-in) are observed. To simulate the experimental behavior, a single degree-offreedom spring mass model is derived, which is based on the information coming from the experimentation. Despite the apparent simplicity, the model is able to catch all the most relevant aspects of the device response. This occurs not only at low values of electrodynamic excitation, but also at higher ones. Nevertheless, the theoretical predictions are not completely fulfilled in some aspects. In particular, the range of existence of each attractor is smaller in practice than in the simulations. This is because, under realistic conditions, disturbances are inevitably encountered (e.g. discontinuous steps when performing the sweeping, approximations in the modeling, etc.) and give uncertainties to the operating initial conditions. A reliable prediction of the actual (and not only theoretical) response is essential in applications. To take disturbances into account, we develop a dynamical integrity analysis. Integrity profiles and integrity charts are performed. They are able to detect the parameter range where each branch can be reliably observed in practice and where, instead, becomes vulnerable. Moreover, depending on the magnitude of the expected disturbances, the integrity charts can serve as a design guideline, in order to effectively operate the device in safe condition, according to the desired outcome. Copyright © 2013 by ASME.

  13. Experimental and theoretical investigation of the first-order hyperpolarizability of a class of triarylamine derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Daniel L., E-mail:, E-mail: [Departamento de Ciências da Natureza, Matemática e Educação, Universidade Federal de São Carlos, Rod. Anhanguera–Km 174, 13600-970 Araras, SP (Brazil); Instituto de Física, Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP (Brazil); Fonseca, Ruben D.; Mendonca, Cleber R.; De Boni, Leonardo, E-mail:, E-mail: [Instituto de Física de São Carlos, Universidade de São Paulo, Caixa Postal 369, 13560-970 São Carlos, SP (Brazil); Vivas, Marcelo G. [Instituto de Ciência de Tecnologia, Universidade Federal de Alfenas, Cidade Universitária - BR 267 Km 533, 37715-400 Poços de Caldas, MG (Brazil); Ishow, E. [CEISAM–UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, 44322 Nantes (France); Canuto, Sylvio [Instituto de Física, Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP (Brazil)


    This paper reports on the static and dynamic first-order hyperpolarizabilities of a class of push-pull octupolar triarylamine derivatives dissolved in toluene. We have combined hyper-Rayleigh scattering experiment and the coupled perturbed Hartree-Fock method implemented at the Density Functional Theory (DFT) level of theory to determine the static and dynamic (at 1064 nm) first-order hyperpolarizability (β{sub HRS}) of nine triarylamine derivatives with distinct electron-withdrawing groups. In four of these derivatives, an azoaromatic unit is inserted and a pronounceable increase of the first-order hyperpolarizability is reported. Based on the theoretical results, the dipolar/octupolar character of the derivatives is determined. By using a polarizable continuum model in combination with the DFT calculations, it was found that although solvated in an aprotic and low dielectric constant solvent, due to solvent-induced polarization and the frequency dispersion effect, the environment substantially affects the first-order hyperpolarizability of all derivatives investigated. This statement is supported due to the solvent effects to be essential for the better agreement between theoretical results and experimental data concerning the dynamic first-order hyperpolarizability of the derivatives. The first-order hyperpolarizability of the derivatives was also modeled using the two- and three-level models, where the relationship between static and dynamic first hyperpolarizabilities is given by a frequency dispersion model. Using this approach, it was verified that the dynamic first hyperpolarizability of the derivatives is satisfactorily reproduced by the two-level model and that, in the case of the derivatives with an azoaromatic unit, the use of a damped few-level model is essential for, considering also the molecular size of such derivatives, a good quantitative agreement between theoretical results and experimental data to be observed.

  14. Experimental and Theoretical Investigation of Sodiated Multimers of Steroid Epimers with Ion Mobility-Mass Spectrometry (United States)

    Chouinard, Christopher D.; Cruzeiro, Vinícius Wilian D.; Roitberg, Adrian E.; Yost, Richard A.


    Ion mobility-mass spectrometry (IM-MS) has recently seen increased use in the analysis of small molecules, especially in the field of metabolomics, for increased breadth of information and improved separation of isomers. In this study, steroid epimers androsterone and trans-androsterone were analyzed with IM-MS to investigate differences in their relative mobilities. Although sodiated monomers exhibited very similar collision cross-sections (CCS), baseline separation was observed for the sodiated dimer species (RS = 1.81), with measured CCS of 242.6 and 256.3 Å2, respectively. Theoretical modeling was performed to determine the most energetically stable structures of solution-phase and gas-phase monomer and dimer structures. It was revealed that these epimers differ in their preferred dimer binding mode in solution phase: androsterone adopts a R=O - Na+ - OH—R' configuration, whereas trans-androsterone adopts a R=O - Na+ - O=R' configuration. This difference contributes to a significant structural variation, and subsequent CCS calculations based on these structures relaxed in the gas phase were in agreement with experimentally measured values (ΔCCS 5%). Additionally, these calculations accurately predicted the relative difference in mobility between the epimers. This study illustrates the power of combining experimental and theoretical results to better elucidate gas-phase structures.

  15. Experimental and theoretical investigation of relative optical band gaps in graphene generations (United States)

    Bhatnagar, Deepika; Singh, Sukhbir; Yadav, Sriniwas; Kumar, Ashok; Kaur, Inderpreet


    Size and chemical functionalization dependant optical band gaps in graphene family nanomaterials were investigated by experimental and theoretical study using Tauc plot and density functional theory (DFT). We have synthesized graphene oxide through a modified Hummer’s method using graphene nanoplatelets and sequentially graphene quantum dots through hydrothermal reduction. The experimental results indicate that the optical band gap in graphene generations was altered by reducing the size of graphene sheets and attachment of chemical functionalities like epoxy, hydroxyl and carboxyl groups plays a crucial role in varying optical band gaps. It is further confirmed by DFT calculations that the π orbitals were more dominatingly participating in transitions shown by projected density of states and the molecular energy spectrum represented the effect of attached functional groups along with discreteness in energy levels. Theoretical results were found to be in good agreement with experimental results. All of the above different variants of graphene can be used in native or modified form for sensor design and optoelectronic applications.

  16. The theoretical investigation of one of the derivatives of 1, 2-dithienylcyclopentene as a molecular switch. (United States)

    Safarpour, Mohammad Ali; Hashemianzadeh, Seyed Majid; Kasaeian, Azam


    The structural and electronic properties of a three-state molecular switch-an active device in a nano-electronic circuit-were studied using the B3LYP/6-31G* method. Due to its chemical stability, high conductivity upon doping, and non-linear optical properties, polythiophene is among the most widely studied conjugated organic polymers, both experimentally and theoretically. The aim of the present work was to theoretically study a very complex case: a three-state switch synthesized and experimentally investigated by Nishida et al. (Org Lett 6:2523-2526, 2004). An initial set of test calculations showed B3LYP level of theory and 6-31G* basis set to be the most appropriate for our purpose, i.e., the study of the structure, charge and spin distributions, as well as electrical characteristics such as electric polarizability, HOMO-LUMO gap (HLG) and electric dipole moment, for one of the 1,2-dithienylcyclopentene derivatives. Also, natural bond orbital analyses were performed to calculate local charges and charge transfers in order to study the capability of the molecule as a molecular switch. The results reported here are of general significance, and demonstrate that it is possible to use certain structural and electrical properties to understand and design electro-photochromic compounds showing a switching function in cases where stable forms can be exchanged by light or electron transfer. Figure Model of a thiophene wire incorporating a redox active unit.

  17. An Experimental and Theoretical Investigation of a Micromirror Under Mixed-Frequency Excitation

    KAUST Repository

    Ilyas, Saad


    We present an experimental and theoretical investigation of a micromachined mirror under a mixed-frequency signal composed of two harmonic ac sources. The micromirror is made of polyimide as the main structural layer. The experimental and theoretical dynamics are explored via frequency sweeps in the desired neighborhoods. One frequency is fixed while the other frequency is swept through a wide range to study the dynamic responses. To simulate the behavior of the micromirror, it is modeled as a single degree of freedom system, where the parameters of the model are extracted experimentally. A good agreement is reported among the simulation results and the experimental data. These responses are studied under different frequencies and input voltages. The results show interesting dynamics, where the system exhibits primary resonance and combination resonances of additive and subtractive type. The mixed excitation is demonstrated as a way to increase the bandwidth of the resonator near primary resonance, which can be promising for resonant sensing applications in the effort to increase the signal-noise ratio over extended frequency range.


    Directory of Open Access Journals (Sweden)

    Sviridov L. T.


    Full Text Available Protective forest plantations, shelter belts and plantings along the highways of Central - Black Earth region and southern Russia are badly damaged, and in some areas destroyed. Therefore, they can not perform their functions and require major reconstruction or restoration. The most resistant and applicable trees and shrubs to create protective forest plantings are: maple, ash, elm species and three-thorned acacia, honey-locust, white and yellow acacia, and other legumes breeds with high drought tolerance, disease resistance, technogenic pollution and pest damage. For the creation and restoration of protective forest plantations we require seeds of these species containing pericarp. In Voronezh State Forestry Academy we have carried out a scientific research for creation of a machine for extracting seeds from the legumes. Analysis of the results of scientific research of prototyping machines showed that they were made without considered technological and mechanical properties of the legumes theoretical researches workflow machines for extracting seeds from the legumes and scientific basis of design parameters and operating modes. In this article we have a presentation of the experimental sample of the machine for extracting seeds from the legumes and theoretical investigation of the workflow in the batch hopper. According to the results of the study, we have obtained a mathematical expression, which allows you to define the parameters and modes of operation of a brush-grater device

  19. Experimental and Theoretical Investigations of Phonation Threshold Pressure as a Function of Vocal Fold Elongation (United States)

    Tao, Chao; Regner, Michael F.; Zhang, Yu; Jiang, Jack J.


    Summary The relationship between the vocal fold elongation and the phonation threshold pressure (PTP) was experimentally and theoretically investigated. The PTP values of seventeen excised canine larynges with 0% to 15% bilateral vocal fold elongations in 5% elongation steps were measured using an excised larynx phonation system. It was found that twelve larynges exhibited a monotonic relationship between PTP and elongation; in these larynges, the 0% elongation condition had the lowest PTP. Five larynges exhibited a PTP minimum at 5% elongation. To provide a theoretical explanation of these phenomena, a two-mass model was modified to simulate vibration of the elongated vocal folds. Two pairs of longitudinal springs were used to represent the longitudinal elastin in the vocal folds. This model showed that when the vocal folds were elongated, the increased longitudinal tension would increase the PTP value and the increased vocal fold length would decrease the PTP value. The antagonistic effects contributed by these two factors were found to be able to cause either a monotonic or a non-monotonic relationship between PTP and elongation, which were consistent with experimental observations. Because PTP describes the ease of phonation, this study suggests that there may exist a nonzero optimal vocal fold elongation for the greatest ease for phonation in some larynges. PMID:25530744

  20. Investigating interactions between phospholipase B-Like 2 and antibodies during Protein A chromatography. (United States)

    Tran, Benjamin; Grosskopf, Vanessa; Wang, Xiangdan; Yang, Jihong; Walker, Don; Yu, Christopher; McDonald, Paul


    Purification processes for therapeutic antibodies typically exploit multiple and orthogonal chromatography steps in order to remove impurities, such as host-cell proteins. While the majority of host-cell proteins are cleared through purification processes, individual host-cell proteins such as Phospholipase B-like 2 (PLBL2) are more challenging to remove and can persist into the final purification pool even after multiple chromatography steps. With packed-bed chromatography runs using host-cell protein ELISAs and mass spectrometry analysis, we demonstrated that different therapeutic antibodies interact to varying degrees with host-cell proteins in general, and PLBL2 specifically. We then used a high-throughput Protein A chromatography method to further examine the interaction between our antibodies and PLBL2. Our results showed that the co-elution of PLBL2 during Protein A chromatography is highly dependent on the individual antibody and PLBL2 concentration in the chromatographic load. Process parameters such as antibody resin load density and pre-elution wash conditions also influence the levels of PLBL2 in the Protein A eluate. Furthermore, using surface plasmon resonance, we demonstrated that there is a preference for PLBL2 to interact with IgG4 subclass antibodies compared to IgG1 antibodies.

  1. Theoretical and numerical investigations of sub-wavelength diffractive optical structures

    DEFF Research Database (Denmark)

    Dridi, Kim


    The work in this thesis concerns theoretical and numerical investigations of sub-wavelength diffractive optical structures, relying on advanced two-dimensional vectorial numerical models that have applications in Optics and Electromagnetics. Integrated Optics is predicted to play a major role...... in future technologies. For this to come true, more advanced optical signal processing must be achieved in miniaturized multifunctional components which should enable optimal light control and light localization. These components have complex subwavelength geometries and material distributions......, such as in dielectric waveguides with gratings and periodic media or photonic crystal structures. The vectorial electromagnetic nature of light is therefore taken into account in the modeling of these diffractive structures. An electromagnetic vector-field model for optical components design based on the classical...

  2. Terahertz Generation in an Electrically Biased Optical Fiber: A Theoretical Investigation

    Directory of Open Access Journals (Sweden)

    Montasir Qasymeh


    Full Text Available We propose and theoretically investigate a novel approach for generating terahertz (THz radiation in a standard single-mode fiber. The optical fiber is mediated by an electrostatic field, which induces an effective second-order nonlinear susceptibility via the Kerr effect. The THz generation is based on difference frequency generation (DFG. A dispersive fiber Bragg grating (FBG is utilized to phase match the two interacting optical carriers. A ring resonator is utilized to boost the optical intensities in the biased optical fiber. A mathematical model is developed which is supported by a numerical analysis and simulations. It is shown that a wide spectrum of a tunable THz radiation can be generated, providing a proper design of the FBG and the optical carriers.

  3. Theoretical and experimental investigations on the nonlinear optical properties of gold(III) dithiolene complexes (United States)

    Guezguez, I.; Karakas, A.; Iliopoulos, K.; Derkowska-Zielinska, B.; El-Ghayoury, A.; Ranganathan, A.; Batail, P.; Migalska-Zalas, A.; Sahraoui, B.; Karakaya, M.


    Degenerate four-wave mixing (DFWM) experiments have been performed to determine the third-order nonlinear optical (NLO) susceptibilities (χ(3)) of gold(III) maleimide dithiolate tetraphenylphosphonium, (PPh4)[Au(midt)2], (Au-P) and gold(III) maleimide dithiolate melamine melaminium hybrid solvate, (C3N6H6)(CNH7+)[Au(midt)2]-·2DMF·2H2O, (Au-Mel). Ab-initio quantum mechanical calculations (time-dependent Hartree-Fock (TDHF) method) of Au-P and Au-Mel have been carried out to compute the electric dipole moment (μ), the dispersion-free and frequency-dependent dipole polarizability (α) and the second hyperpolarizability (γ) values. These theoretical calculations are in good agreement with the experimentally obtained results by the DFWM technique. All the investigations show clearly the effect played by the counter ion on the resulting NLO properties of the two gold complexes.

  4. Catecholase activity investigations using in situ copper complexes continuing Schiff base derivatives with a theoretical calculation

    Directory of Open Access Journals (Sweden)

    A. Djedouani


    Full Text Available The study of catecholase activity of a series of Schiff base compounds using in situ copper complexes of 4-hydroxy-6-methyl-3-(1-(phenyliminoethyl-2H-pyran-2-one derivatives has been reported. The reaction rate depends on four parameters: The nature of the substitution in para position to the benzene ring, the nature of counter anion, the concentration of ligand and the nature of solvent. The highest rate activity is given by complex resulting from one equivalent of ligand L2 and two equivalents of copper acetate in methanol, which equal to 62.25 µmol.min-1.L-1.In other part, a theoretical study of such ligands using the semi-empirical method AM1 were also investigated. A good relationship founded between the maximal reaction rate (Vmax and the HOMO energy (Pearson correlation: r=-0.794.

  5. Theoretical and experimental investigations on the match between pulse tube cold fingers and linear compressors (United States)

    Tan, Jun; Dang, Haizheng; Zhang, Lei


    The match between the cold finger and the linear compressor of the Stirling-type pulse tube cryocooler plays a vital role in optimizing the compressor efficiency and in improving the cold finger cooling performance. To reveal the match mechanism between the linear compressor and pulse tube cold finger (PTCF), detailed analyses have been made to understand the interactions between them. Based on the theoretical investigations, both of the design method of the PTCF to match the given linear compressor and a reverse method of the linear compressor to match the given PTCF have been proposed. In order to verify the validity of these theories and methods, actual PTCF and linear compressor are developed to match the existing linear compressor and PTCF, respectively. The experimental results show good agreements with the simulated ones.

  6. Theoretical investigation of antiferroelectric (SmCA*) subphases by hydrodynamical approach (United States)

    Lahiri, T.; Pal Majumder, T.


    We provide a hydrodynamical approach utilizing time dependent Landau-Ginzburg model (L-G) and the Cahn-Hilliard model (C-H) to investigate antiferroelectric liquid crystals (AFLCs) exhibiting different chiral phases between paraelectric smectic A (SmA*) phase and antiferroelectric smectic CA* phase (SmCA*). Introducing conserved and non-conserved order parameters in C-H and L-G models, we have predicted the appearance of a chiral smectic C (SmC*) phase and a ferrielectric SmCFI1* phase (three layers SmCA*) in an antiferroelectric phase sequence. The three layers periodicity for SmCFI1* phase is studied in detail with a non-uniform layer interactions among smectic layers with strong experimental support. Finally, we provide some theoretical basis for the non-uniformity of our proposed layer interactions.

  7. Theoretical investigation of polarization effects in solution: Importance of solvent collective motions

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, Tateki [Department of Theoretical and Computational Molecular Science, Institute for Molecular Science Myodaiji, Okazaki 444-8585, Aichi (Japan)


    Recent theoretical studies on interesting topics related to polarization effects in solutions are presented. As one of interesting topics, ionic liquids (ILs) solvents are focused on. The collective dynamics of electronic polarizability through interionic dynamics and the effect of polarization in ILs, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF{sub 6}]), are studied with molecular dynamics simulation. Also, the time-dependent polarization effect on the probe betaine dye molecule, pyridinium N-phenoxide, in water is investigated by a time-dependent reference interaction site model self-consistent field (time-dependent RISM-SCF) approach. The importance of considering polarization effects on solution systems related to solvent collective motions is shown.

  8. Theoretical investigation of three-dimensional quasi-phase-matching photonic structures (United States)

    Pogosian, Tamara; Lai, Ngoc Diep


    We present a full theoretical analysis of quasi-phase-matching (QPM) in three-dimensional (3D) periodic structures and point up optimum nonlinear structures, which promote the best nonlinear conversion efficiencies and are close to real structures. The QPM properties of 14 Bravais lattices are investigated as a function of motifs (orthorhombic and spherical) and of modulation types ("+/-" and "+/0"). This full 3D QPM theory allows us to produce all results of one- and two-dimensional QPM structures by choosing appropriate lattice periodicity and motif. The optimization of nonlinear conversion efficiencies in 3D QPM is obtained by analyzing four particular structures (simple cubic, body-centered cubic, face-centered cubic, and diamond cubic lattices) with different filling factors and motifs. In particular, 3D structures, which are very close to those realized in practice, are proposed and simulated, creating a guide for fabrication of real optimum QPM structures.

  9. Theoretical and experimental investigation of fiber Bragg gratings with different lengths for ultrasonic detection (United States)

    Yu, Zhouzhou; Jiang, Qi; Zhang, Hao; Wang, Junjie


    In this paper, the response of fiber Bragg gratings (FBGs) subjected to the ultrasonic wave has been theoretically and experimentally investigated. Although FBG sensors have been widely used in the ultrasonic detection for practical structural health monitoring, the relationship between the grating length and ultrasonic frequency is not yet to be obtained. To address this problem, an ultrasound detection system based on FBGs is designed and the response sensitivity of different lengths gratings are detected. Experimental results indicate that the grating with 3 mm length has a higher sensitivity when detecting high frequency ultrasonic wave, and the amplitude can be up to 0.6 mV. The 10 mm length grating has better detection sensitivity for low frequency ultrasonic wave and the amplitude is 0.8 mV. The results of this analysis provide useful tools for high sensitivity ultrasound detection in damage detection systems.

  10. Theoretical Investigation of Nonlinear Optical Properties of Organic and Transition Metal Hybrid Azobenzene Dendrimers

    Institute of Scientific and Technical Information of China (English)

    LIU Cai-Ping; LIU Ping; WU Ke-Chen


    In this work, we report a theoretical exploration of the responses of organic azo-benzene dendrimers. The polarizabilities, the first and second hyperpolarizabilities of the azobenzene monomers (GO), and the first, second and third generation (G1, G2 and G3, respectively) are investigated by semi-empirical methods. The calculated results show that the nonlinear optical (NLO)properties of these organic dendrimers are mainly determined by the azobenzene chromospheres.Additionally, the values of β and γ increase almost in proportion to the number of chromophores. On the other hand, two types of transition metal hybrid azobenzene dendrimers (core-hybrid and branch-end hybrid according to the sites combined with transition metals) are simulated and discussed in detail in the framework of time-dependent density functional theory (TDDFT). The calculated results reveal that the NLO responses of these metal dendrimers distinctly varied as a result of altering the charge transfer transition scale and the excitation energies.

  11. Corrosion product deposits on boiling-water reactor cladding: Experimental and theoretical investigation of magnetic properties (United States)

    Orlov, A.; Degueldre, C.; Wiese, H.; Ledergerber, G.; Valizadeh, S.


    Recent Eddy current investigations on the cladding of nuclear fuel pins have shown that the apparent oxide layers are falsified due to unexpected magnetic properties of corrosion product deposits. Analyses by Scanning Electron Microscopy (SEM) or Electron Probe Micro Analysis (EPMA) demonstrated that the deposit layer consists of complex 3-d element oxides (Ni, Mn, Fe) along with Zn, since the reactor operates with a Zn addition procedure to reduce buildup of radiation fields on the recirculation system surfaces. The oxides crystallise in ferritic spinel structures. These spinels are well-known for their magnetic behaviour. Since non-magnetic zinc ferrite (ZnFe 2O 4) may become magnetic when doped with even small amounts of Ni and/or Mn, their occurrence in the deposit layer has been analyzed. The magnetic permeability of zinc ferrite, trevorite and jacobsite and their solid solutions are estimated by magnetic moment additivity. From the void history examination, the low elevation sample (810 mm) did not face significant boiling during the irradiation cycles suggesting growth of (Mn0.092+Zn0.752+Fe0.293+)[(Fe1.713+Mn0.032+Ni0.132+)O] crystals with theoretical value of the magnetic permeability for the averaged heterogeneous CRUD layer of 9.5 ± 3. Meanwhile, (Mn0.162+Zn0.552+Fe0.293+)[(Fe1.713+Mn0.042+Ni0.252+)O] crystallizes at the mid elevation (1810 mm) with theoretical magnetic permeability for the CRUD layer of 4.2 ± 1.5 at the investigated azimuthal location. These theoretical data are compared with the magnetic permeability of the corrosion product deposited layers gained from reactor pool side Eddy current (EC) analyses (9.0 ± 1.0 for low and 3.5 ± 1.0 for high elevation). The calculated thicknesses and magnetic permeability values of the deposition layers (estimated by MAGNACROX multifrequency EC method) match together with these estimated using an "ion magnetic moment additivity" model.

  12. Investigation of isomeric flavanol structures in black tea thearubigins using ultraperformance liquid chromatography coupled to hybrid quadrupole/ion mobility/time of flight mass spectrometry. (United States)

    Yassin, Ghada H; Grun, Christian; Koek, Jean H; Assaf, Khaleel I; Kuhnert, Nikolai


    Ultra performance liquid chromatography (UPLC) when coupled to ion mobility (IMS)/orthogonal acceleration time of flight mass spectrometry is a suitable technique for analyzing complex mixtures such as the black tea thearubigins. With the aid of this advanced instrumental analysis, we were able to separate and identify different isomeric components in the complex mixture which could previously not be differentiated by a conventional high performance liquid chromatography/tandem mass spectrometry. In this study, the difference between isomeric structures theasinensins, proanthocyanidins B-type and rutin (quercetin-3O-rutinoside) were studied, and these are present abundantly in many botanical sources. The differentiation between these structures was accomplished according to their acquired mobility drift times differing from the traditional investigations in mass spectrometry, where calculation of theoretical collisional cross sections allowed assignment of the individual isomeric structures. The present work demonstrates UPLC-IMS-MS as an efficient technology for isolating and separating isobaric and isomeric structures existing in complex mixtures discriminating between them according to their characteristic fragment ions and mobility drift times. Therefore, a rational assignment of isomeric structures in many phenolic secondary metabolites based on the ion mobility data might be useful in mass spectrometry-based structure analysis in the future.

  13. Theoretical Investigation and Experimental Verification of Passive Simulation of Metal Plate Infrared Thermal Characteristics with That of PCM

    Institute of Scientific and Technical Information of China (English)


    A one-dimensional thermophysical model is used to investigate the simulation of the infrared thermal signature of mental plate with phase change material(PCM) plate theoretically. The optimized parameters are obtained by the theoretical calculations. Based on the calculation results, a kind of organic PCM is selected to experimentally verify the model, and the good match between the theoretical and experimental results is achieved. The results of this investigation provide the design rules and key materials for the application of PCMs in false target.

  14. Theoretical investigation of triphenylamine-based sensitizers with different π-spacers for DSSC. (United States)

    Li, Wei; Wang, Jian; Chen, Jie; Bai, Fu-Quan; Zhang, Hong-Xing


    The molecular geometries, electronic structures, and absorption spectra of two organic dyes, 3-(5-(4-(IDB)phenyl)thiophene-2-yl)-2-cyanoacrylic acid (IDB-1), and 3-(5-(4-(IDB)styryl) thiophene-2-yl)-2-cyanoacrylic acid (IDB-2), before and after binding to TiO2 cluster were investigated by density functional theory (DFT) and time-dependent DFT (TDDFT) methods to understand the effect of enhanced π-conjugation of organic dye on the energy-to-electricity conversion efficiency (η) of dye-sensitized solar cell (DSSC), where, IDB=10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl. The introduction of vinyl unit into the π-spacer enhances the coplanarity and subsequently red-shifts, intensifies, and broadens the absorption spectrum of IDB-2, resulting in the stronger electronic coupling between dye and TiO2 conduction band, thus the more efficient electron transfer. From the theoretical evaluation of electron injection driving force (D), light-harvesting efficiency (LHE), and shift of TiO2 conduction band (ΔEcb), we successfully interpreted the experimentally observed efficiency difference between IDB-1 and IDB-2. Under this theoretical procedure, several novel D-π-A dyes namely IDB-3, IDB-4, and IDB-5, were designed. Our calculated results reveal that IDB-5 has the improved Jsc and Voc compared with IDB-2 because it performs nicely on the three key parameters (D, LHE, and ΔEcb). This work highlight the importance of using dimethyl-substituted cyclopentadithiophene group as π-spacer in achieving more efficient dyes for DSSC. We hope these discussions can provide fundamental guidelines for the optimization of existing cell efficiency as well as the design of novel high-efficiency organic dyes.

  15. Theoretical Investigation on Skin Effect Factor of Conductor in Power Cables (United States)

    Suzuki, Hiroshi; Kanaoka, Mamoru

    This paper describes a newly-derived theoretical equation on the skin effect factor of power cables, and its application to large-size OF and XLPE cables with segmental conductors, including insulated wires. The skin effect factors calculated with the new equation were fit very well to measurements in wide range conductor sizes. In the new equation, the important factor which characterizes the skin effect of segmental conductors is the `equivalent conductivity ratio' ν defined by the ratio of longitudinal conductivity in axial direction of conductor to conductivity of conductor wires. Since the obtained ratio ν in XLPE cable was three times greater than that in OF cable, the larger longitudinal eddy current passing from a wire to another increased the eddy current loss in conductor, which increased the conductor loss of XLPE cable. The new equation enables us to investigate quantitatively the dominant loss component affecting the skin effect factor. Then, the skin effect factors and coefficients for OF and XLPE cables were investigated with the new equation. It was revealed that the best number of separation, in which the skin effect became minimum, existed in OF and XLPE cables with segmental conductors. In addition, it was confirmed that the skin effect coefficients ks1 calculated with the new equation were consistent well with those used in JCS.

  16. Addition Mechanisms of Phenol toward Formaldehyde under Acidic Condition: a Theoretical Investigation

    Institute of Scientific and Technical Information of China (English)

    XU Wen-Feng; XIONG Shan-Shan; SHI Yu-Qing; LI Tao-Hong; DU Guan-Ben; XIE Xiao-Guang


    The reaction mechanisms of phenol with formaldehyde in the first and second addition at the ortho- and para-position in acid solution were theoretically investigated at the PW91/DNP level with solvent effects included. The reaction of phenol with protonated methanediol firstly forms an adduct intermediate, via a SN2 mechanism with a water molecule as the leaving group. From the adduct intermediate, there are two reaction channels involving a proton transfer to form the addition products. One is that a proton directly transfers via a four-membered ring transition state with a notable energy barrier (Four-member mechanism). Another mechanism involving a water molecule as catalyst to mediate the proton transfer (WCP mechanism), is a barrierless process, indicating that the formation of the adduct intermediate, the first reaction step, is rate-limiting. The reaction products are free hydroxymethyl phenols and/or hydroxybenzy carbocation (HOC6H4CH2+) which plays an important role in the following formation of methylene and methylene ether linkages. The second addition reactions between formaldehyde and hydroxymethyl phenol at all possible reaction sites of the phenol ring in acid solution were also investigated and discussed.

  17. Theoretical investigation of interaction between the set of ligands and α7 nicotinic acetylcholine receptor (United States)

    Glukhova, O. E.; Prytkova, T. R.; Shmygin, D. S.


    Nicotinic acetylcholine receptors (nAChRs) are neuron receptor proteins that provide a transmission of nerve impulse through the synapses. They are composed of a pentametric assembly of five homologous subunits (5 α7 subunits for α7nAChR, for example), oriented around the central pore. These receptors might be found in the chemical synapses of central and peripheral nervous system, and also in the neuromuscular synapses. Transmembrane domain of the one of such receptors constitutes ion channel. The conductive properties of ion channel strongly depend on the receptor conformation changes in the response of binding with some molecule, f.e. acetylcholine. Investigation of interaction between ligands and acetylcholine receptor is important for drug design. In this work we investigate theoretically the interaction between the set of different ligands (such as vanillin, thymoquinone, etc.) and the nicotinic acetylcholine receptor (primarily with subunit of the α7nAChR) by different methods and packages (AutodockVina, GROMACS, KVAZAR, HARLEM, VMD). We calculate interaction energy between different ligands in the subunit using molecular dynamics. On the base of obtained calculation results and using molecular docking we found an optimal location of different ligands in the subunit.

  18. Theoretical investigation of loratadine reactivity in order to understand its degradation properties: DFT and MD study. (United States)

    Armaković, Stevan; Armaković, Sanja J; Abramović, Biljana F


    Antihistamines are frequently used pharmaceuticals that treat the symptoms of allergic reactions. Loratadine (LOR) is an active component of the second generation of selective antihistaminic pharmaceutical usually known as Claritin. Frequent usage of this type of pharmaceuticals imposes the need for understanding their fundamental reactive properties. In this study we have theoretically investigated reactive properties of LOR using both density functional theory (DFT) calculations and molecular dynamics (MD) simulations. DFT study is used for collecting information related to the molecule stability, structure, frontier molecular orbitals, quantum molecular descriptors, charge distribution, molecular electrostatic potential surfaces, charge polarization, and local reactivity properties according to average local ionization energy surfaces. Based on these results, N24 atom of pyridine ring and oxygen atom O1 were identified with nucleophilic nature. In order to collect the information necessary for the proposition of degradation compounds we also calculated bond dissociation energies (BDE) for hydrogen abstraction and single acyclic bonds as well. According to BDE, the oxidation is likely to occur in the piperidine and cycloheptane rings. MD simulations were used in order to understand the interactions with water through radial distribution functions (RDF). Based on RDFs the most important interactions with solvent are determined for carbon atom C5, chlorine atom Cl15, and oxygen atom O1. Collected results based on DFT calculations and MD simulations provided information important for suggestion of possible degradation compounds. Covalent and noncovalent interactions between LOR and (•)OH have also been investigated.

  19. Development of a capillary plasma pump with vapour bubble for water purification: experimental and theoretical investigation (United States)

    Uehara, S.; Ishihata, K.; Nishiyama, H.


    This paper describes the development of a small-sized reactive plasma pump driven by capillary bubble discharge for the purification of treated water. The apparatus we developed decomposes the pollutants in the water by using chemical species generated by the plasma discharge. The resulting stream of bubbles obviates the need for an external gas supply or pump to transport the water. A high-speed camera was used to investigate the bubble dynamics responsible for the pumping effect, which is achieved by selecting the shape of the capillary such that the bubble ejections within enhance the ‘self-repetition’ action required for the pumping motion. Our experiments showed that optimal bubble generation requires a consumed power of 17.8 W. A theoretical model was developed to investigate the pumping mechanism. We solve the problems associated with liquid oscillations in the U-shaped water reservoir by employing a non-uniform cross-sectional area in our model. The chemical reactivity of the device was confirmed by using emission spectroscopy of OH radical and by measuring the decomposition of methylene blue.

  20. Adsorption of Emerging Munitions Contaminants on Cellulose Surface: A Combined Theoretical and Experimental Investigation. (United States)

    Shukla, Manoj K; Poda, Aimee


    This manuscript reports results of an integrated theoretical and experimental investigation of adsorption of two emerging contaminants (DNAN and FOX-7) and legacy compound TNT on cellulose surface. Cellulose was modeled as trimeric form of the linear chain of 1 → 4 linked of β-D-glucopyranos in (4)C1 chair conformation. Geometries of modeled cellulose, munitions compounds and their complexes were optimized at the M06-2X functional level of Density Functional Theory using the 6-31G(d,p) basis set in gas phase and in water solution. The effect of water solution was modeled using the CPCM approach. Nature of potential energy surfaces was ascertained through harmonic vibrational frequency analysis. Interaction energies were corrected for basis set superposition error and the 6-311G(d,p) basis set was used. Molecular electrostatic potential mapping was performed to understand the reactivity of the investigated systems. It was predicted that adsorbates will be weakly adsorbed on the cellulose surface in water solution than in the gas phase.

  1. Vibrational spectroscopy and aromaticity investigation of squarate salts: A theoretical and experimental approach (United States)

    Georgopoulos, Stéfanos L.; Diniz, Renata; Yoshida, Maria I.; Speziali, Nivaldo L.; Santos, Hélio F. Dos; Junqueira, Geórgia Maria A.; de Oliveira, Luiz F. C.


    Experimental and theoretical investigations of squarate salts [M 2(C 4O 4)] (M=Li, Na, K and Rb) were performed aiming to correlate the structures, vibrational analysis and aromaticity. Powder X-ray diffraction data show that these compounds are not isostructural, indicating that the metal-squarate and hydrogen bonds to water molecules interactions play a significant role on the the crystal packing. The infrared and Raman assigments suggest an equalization of the C-C bond lengths with the increasing of the counter-ion size. This result is interpreted as an enhancement in the electronic delocalization and consequently in the degree of aromaticity for salts with larger ions. Quantum mechanical calculations for structures, vibrational spectra and aromaticity index are in agreement with experimental finding, giving insights at molecular level for the role played by distinct complexation modes to the observed properties. Comparison between our results and literature, regarding molecular dynamics in different chemical environments, shows that aromaticity and hydrogen bonds are the most important forces driving the interactions in the solid structures of squarate ion.

  2. Theoretical investigation on nonlinear optical effects in laser trapping of dielectric nanoparticles with ultrafast pulsed excitation. (United States)

    Devi, Anita; De, Arijit K


    The use of low-power high-repetition-rate ultrafast pulsed excitation in stable optical trapping of dielectric nanoparticles has been demonstrated in the recent past; the high peak power of each pulse leads to instantaneous trapping of a nanoparticle with fast inertial response and the high repetition-rate ensures repetitive trapping by successive pulses However, with such high peak power pulsed excitation under a tight focusing condition, nonlinear optical effects on trapping efficiency also become significant and cannot be ignored. Thus, in addition to the above mentioned repetitive instantaneous trapping, trapping efficiency under pulsed excitation is also influenced by the optical Kerr effect, which we theoretically investigate here. Using dipole approximation we show that with an increase in laser power the radial component of the trapping potential becomes progressively more stable but the axial component is dramatically modulated due to increased Kerr nonlinearity. We justify that the relevant parameter to quantify the trapping efficiency is not the absolute depth of the highly asymmetric axial trapping potential but the height of the potential barrier along the beam propagation direction. We also discuss the optimal excitation parameters leading to the most stable dipole trap. Our results show excellent agreement with previous experiments.

  3. Theoretical and Experimental Investigations on Droplet Evaporation and Droplet Ignition at High Pressures (United States)

    Ristau, R.; Nagel, U.; Iglseder, H.; Koenig, J.; Rath, H. J.; Normura, H.; Kono, M.; Tanabe, M.; Sato, J.


    The evaporation of fuel droplets under high ambient pressure and temperature in normal gravity and microgravity has been investigated experimentally. For subcritical ambient conditions, droplet evaporation after a heat-up period follows the d(exp 2)-law. For all data the evaporation constant increases as the ambient temperature increases. At identical ambient conditions the evaporation constant under microgravity is smaller compared to normal gravity. This effect can first be observed at 1 bar and increases with ambient pressure. Preliminary experiments on ignition delay for self-igniting fuel droplets have been performed. Above a 1 s delay time, at identical ambient conditions, significant differences in the results of the normal and microgravity data are observed. Self-ignition occurs within different temperature ranges due to the influence of gravity. The time dependent behavior of the droplet is examined theoretically. In the calculations two different approaches for the gas phase are applied. In the first approach the conditions at the interface are given using a quasi steady theory approximation. The second approach uses a set of time dependent governing equations for the gas phase which are then evaluated. In comparison, the second model shows a better agreement with the drop tower experiments. In both cases a time dependent gasification rate is observed.

  4. Pinning of thermal excitations at defects in artificial dipolar arrays: A theoretical investigation

    Energy Technology Data Exchange (ETDEWEB)

    Thonig, D., E-mail: [Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 21 Uppsala (Sweden); Henk, J. [Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06120 Halle (Saale) (Germany)


    In this theoretical investigation we address the effect of defects on thermal excitations in square-lattice dipolar arrays. The samples consist of nanomagnets, whose geometry is adopted from recent experiments [A. Farhan et al., Nat. Phys. 9 (2013) 375] [13] and allows for thermal activation at room temperature. Various types of defects, all of which may be produced by microstructuring techniques, are introduced into the systems. It turns out that excitations can efficiently be pinned at defects. Furthermore, it is possible to produce ferromagnetic strings of nanomagnets that connect a pair of defects; their lengths are closely related to the distance of the defects and the topology of the magnetic ground-state configuration. - Highlights: • We model various types of defects in square-lattice dipolar arrays. • We examine, especially, the correlation between the defects, all of which may be produced by microstructuring techniques. • Thermal excitations in square-lattice dipolar arrays can effectively be pinned at defects. • Ferromagnetic strings of nanomagnets can be produced by pairs of defects, where the length is closely related to the distance of the defects.

  5. Theoretical investigation of manganese adsorption on graphene and graphane: A first-principles comparative study

    Energy Technology Data Exchange (ETDEWEB)

    AlZahrani, A.Z., E-mail: [Physics department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia)


    Within the framework of spin-polarized generalized gradient approximation ({sigma}GGA) of the density functional theory (DFT) and pseudopotential method, the structural, magnetic, and electronic properties of graphene and graphane upon the adsorption of manganese atoms have been theoretically investigated. In contrast to the recent results (New J. Phys. 12, 063020 (2010)), Mn atom has been found to be adsorbed on a hollow-site configuration and no appreciable indication to substitute one of the C atoms of the graphene sheet. Unlike the recent results on Mn-doped graphane (Carbon 48, 3901 (2010)), the Mn adatom prefers to adsorb on the top of a carbon atom, forming a bridge with the uppermost hydrogen atoms. The magnetic moment of the Mn-doped graphene is found to be larger than that of the Mn-doped graphane. The structural parameters and electronic properties of both Mn-doped graphene and Mn-doped graphane are determined and compared with the available data.

  6. Theoretical investigation of the precipitation of δ' in Al-Li (United States)

    Khachaturyan, A. G.; Lindsey, T. F.; Morris, J. W.


    This paper contains the results of a theoretical investigation of the equilibrium between a disordered fee solution and an Ll2 phase in a model binary alloy and the transformation paths that may be followed when the disordered phase is quenched into the two-phase field. The results are specifically applied to binary Al-Li alloys, in which case the ordered phase is the metastable Al3Li (δ') phase that precipitates from the disordered solid solution (α). The thermodynamic model assumes that the atoms interact in pairs with an interaction potential that is independent of the temperature and composition, and uses the “mean field approximation” for the entropy of mixing. The assumptions confine its applicability to temperatures well below the ordering temperature of the Ll2 phase. The model is used to compute the two-phase field that separates the disordered solution and the Ll2 phase. For the specific case of Al-Li, it provides results that fit the available experimental data and offer a simple explanation for the observed deviation from stoichiometry of the δ' phase. The model predicts that the disordered solution orders congruently on quenching, but is then unstable with respect to decom-position by a spinodal mechanism that leads ultimately to a state of ordered Ll2 precipitates in a disordered matrix. The results provide plausible interpretations for the transformations observed in quenched Al-Li alloys.

  7. Experimental and theoretical investigation of the drilling of alumina ceramic using Nd:YAG pulsed laser (United States)

    Hanon, M. M.; Akman, E.; Genc Oztoprak, B.; Gunes, M.; Taha, Z. A.; Hajim, K. I.; Kacar, E.; Gundogdu, O.; Demir, A.


    Alumina ceramics have found wide range of applications from semiconductors, communication technologies, medical devices, automotive to aerospace industries. Processing of alumina ceramics is rather difficult due to its high degree of brittleness, hardness, low thermal diffusivity and conductivity. Rapid improvements in laser technologies in recent years make the laser among the most convenient processing tools for difficult-to-machine materials such as hardened metals, ceramics and composites. This is particularly evident as lasers have become an inexpensive and controllable alternative to conventional hole drilling methods. This paper reports theoretical and experimental results of drilling the alumina ceramic with thicknesses of 5 mm and 10.5 mm using milisecond pulsed Nd:YAG laser. Effects of the laser peak power, pulse duration, repetition rate and focal plane position have been determined using optical and Scanning Electron Microscopy (SEM) images taken from cross-sections of the drilled alumina ceramic samples. In addition to dimensional analysis of the samples, microstructural investigations have also been examined. It has been observed that, the depth of the crater can be controlled as a function of the peak power and the pulse duration for a single laser pulse application without any defect. Crater depth can be increased by increasing the number of laser pulses with some defects. In addition to experimental work, conditions have been simulated using ANYS FLUENT package providing results, which are in good agreement with the experimental results.

  8. Molecular-orbital and structural descriptors in theoretical investigation of electroreduction of nitrodiazoles

    Directory of Open Access Journals (Sweden)



    Full Text Available It is shown how a simple theoretical approach can be used for the investigation of electro-organic reactions.Mononitroimidazoles and mononitropyrazoles were studied by the semiempirical MNDO-PM3 molecular orbital method. The electrochemical reduction potentials of diazoles have been correlated with the energy of the lowest unoccupied molecular orbital (LUMO. It was found that an admirable correlation could be obtained by the introduction of simple structural descriptors as a correction to the energy of the LUMO. The interaction of a molecule with its surrounding depends on electrostatic potential and on steric hindrance. Most of these steric effects are taken into account using two parameters having a very limited set of integer values. The first (b is the position of a ring substituent regarding ring nitrogens, which accounts for the different orientations of dipole moments and for the different shape of the electrostatic potential. The second (structural parameter (t is the type of the ring, which accounts mostly for different modes of electrode approach, and for different charge polarization patterns in two diazole rings. The extended correlation with ELUMO, b and t, is very good, having a regression coefficient r = 0.991. The intrinsic importance of b and t is exemplified by their high statistical weight.

  9. Structural, electronic and optical properties of Cu-doped ZnO: experimental and theoretical investigation (United States)

    Horzum, S.; Torun, E.; Serin, T.; Peeters, F. M.


    Experiments are supplemented with ab initio density functional theory (DFT) calculations in order to investigate how the structural, electronic and optical properties of zinc oxide (ZnO) thin films are modified upon Cu doping. Changes in characteristic properties of doped thin films, that are deposited on a glass substrate by sol-gel dip coating technique, are monitored using X-ray diffraction (XRD) and UV measurements. Our ab initio calculations show that the electronic structure of ZnO can be well described by DFT+U/? method and we find that Cu atom substitutional doping in ZnO is the most favourable case. Our XRD measurements reveal that the crystallite size of the films decrease with increasing Cu doping. Moreover, we determine the optical constants such as refractive index, extinction coefficient, optical dielectric function and optical energy band gap values of the films by means of UV-Vis transmittance spectra. The optical band gap of ZnO the thin film linearly decreases from 3.25 to 3.20 eV at 5% doping. In addition, our calculations reveal that the electronic defect states that stem from Cu atoms are not optically active and the optical band gap is determined by the ZnO band edges. Experimentally observed structural and optical results are in good agreement with our theoretical results.

  10. Theoretical and experimental investigation of acoustic streaming in a porous material. (United States)

    Poesio, Pietro; Ooms, Gijs; Schraven, Arthur; van der Bas, Fred


    An experimental and theoretical investigation of the influence of high-frequency acoustic waves on the flow of a liquid through a porous material has been made. Particular attention was paid to the phenomenon of acoustic streaming of the liquid in the porous material due to the damping of the acoustic waves. The experiments were performed on Berea sandstone cores. Two acoustic horns were used with frequencies of 20 and 40 kHz, and with maximum power output of 2 and 0.7 kW, respectively. A high external pressure was applied in order to avoid cavitation. A microphone was used to measure the damping of the waves in the porous material and also temperature and pressure measurements in the flowing liquid inside the cores were carried out. To model the acoustic streaming effect Darcy's law was extended with a source term representing the momentum transfer from the acoustic waves to the liquid. The model predictions for the pressure distribution inside the core under acoustic streaming conditions are in reasonable agreement with the experimental data.

  11. Experimental and theoretical investigations of the adhesion time of Penicillium spores to cedar wood surface. (United States)

    Soumya, Elabed; Ibnsouda, Saad Koraichi; Abdellah, Houari; Hassan, Latrache


    In this study, the adhesion of 4 Penicillium strains (Penicillium granulatum, Penicillium crustosum, Penicillium commune and Penicillium chrysogenum) on cedar wood was examined qualitatively and quantitatively by using the extended DLVO (XDLVO) approach and the environmental scanning electronic microscopy (ESEM) technique. A comparison between the XDLVO theories and the ESEM technique was also investigated. The adhesion tests revealed that P. chrysogenum was not able to adhere on the cedar wood substrata, as predicted by the XDLVO approach. We have also found by ESEM that the three Penicillium strains (P. granulatum, P. crustosum, P. commune) adhered on wood, as not predicted theoretically. Moreover, the time of adhesion (3 h and 24 h) was used not only to compare the capacity of adhesion according to contact time but also to explain the discrepancies between the XDLVO approach prediction and the adhesion experiments. A positive relationship between the XDLVO approach and adhesion experiments has been observed after 3h of adhesion. In contrast, a contradiction between the XDLVO predictions and the adhesion test results has been noted after 24h of adhesion of Penicillium strains to the wood surface.

  12. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    Energy Technology Data Exchange (ETDEWEB)

    Vlassa, Mihaela, E-mail: [' ' Babes-Bolyai' ' University, Raluca Ripan Institute of Research in Chemistry, 30 Fantanele Str., 400294 Cluj-Napoca (Romania); Bende, Attila, E-mail: [Molecular and Biomolecular Physics Department, National Institute for Research and Development of Isotopic and Molecular Technologies, Str. Donat 67-103, Cluj Napoca RO-400293 (Romania)


    Highlights: • Ni(II)- and Zn(II)-coordinated cyclam–azorubine complexes are described using DFT. • Ni(II) coordinated system shows a reasonably small singlet–triplet energy gap. • Intersystem crossing gives high barrier between singlet and triplet geometries. • For the Zn(II) case only the singlet state is energetically favorable. • The stability of a longer polymer (oligomer) chain was described using DFTB. - Abstract: Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet–triplet transition was studied in details and the corresponding spin–orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  13. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex (United States)

    Vlassa, Mihaela; Bende, Attila


    Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet-triplet transition was studied in details and the corresponding spin-orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  14. Experimental and theoretical investigation of vibrational spectra of coordination polymers based on TCE-TTF. (United States)

    Olejniczak, Iwona; Lapiński, Andrzej; Swietlik, Roman; Olivier, Jean; Golhen, Stéphane; Ouahab, Lahcène


    The room-temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7-tetrakis(2-cyanoethylthio)-tetrathiafulvalene (TCE-TTF) with paramagnetic (Co(II), Mn(II)) and diamagnetic (Zn(II), Cd(II)) ions, together with BF(4)(-) or ClO(4)(-) anions are reported. Infrared and Raman-active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE-TTF using density functional theory (DFT) methods. It is confirmed that the TCE-TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C=C stretching vibrations of TCE-TTF are analyzed assuming the occurrence of electron-molecular vibration coupling (EMV). The presence of the antisymmetric C=C dimeric mode provides evidence that charge transfer takes place between TCE-TTF molecules belonging to neighboring polymeric networks.

  15. Theoretical investigation on thermoelectric properties of Cu-based chalcopyrite compounds (United States)

    Wang, Biao; Xiang, Hongjun; Nakayama, Tsuneyoshi; Zhou, Jun; Li, Baowen


    Cu-based materials are potential candidates for commercial thermoelectric materials due to their abundance, nontoxicity, and high performance. We incorporate the multiband Boltzmann transport equations with first-principles calculations to theoretically investigate the thermoelectric properties of Cu-based chalcopyrite compounds. As a demonstration of our method, the thermoelectric properties of quaternary compounds Cu2ZnSnX4 (X = S, Se) and ternary compounds CuBTe2 (B = Ga, In) are studied. We systematically calculate the electrical conductivity, the Seebeck coefficient, and the power factor of the four materials above based on parameters obtained from first-principles calculations and using several other fitting parameters. For quaternary compounds, our results reveal that Cu2ZnSnSe4 is better than Cu2ZnSnS4 and its optimal hole concentration is around 5 ×1019cm-3 with the peak power factor 4.7 μ W/cm K 2 at 600 K. For ternary compounds, we find that their optimal hole concentrations are around 1 ×1020cm-3 with the peak power factors over 26 μ W/cm K 2 at 800 K.

  16. Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Liang; Xie, Yun [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Du, Liang [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); School of Radiation Medicine and Protection (SRMP), School for Radiological and Interdisciplinary Sciences (RAD-X), Suzhou 215000 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Tan, Zhaoyi, E-mail: [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)


    Highlights: • This is the first theoretical investigation about T–H exchange in vacuum oil. • T–H isotope exchange is accomplished through two different change mechanisms. • Isotope exchange is selective, molecules with −OH and −COOH exchange more easily. • The methyl and methylene radicals in waste oil were observed by {sup 1}HNMR. - Abstract: The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium–hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T–H exchange mechanism and the hyrogenation–dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation–dehydrogenation exchange mechanism, the T–H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with −OH and −COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T–H isotope exchange can be determined by the hydrogenation of T{sub 2} or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products.

  17. Theoretical investigation of heave dynamics of an air cushion vehicle bag and finger skirt (United States)

    Chung, Joon

    This thesis describes a theoretical investigation of the nonlinear and linear heave dynamics of an air cushion vehicle (ACV) equipped with a bag and finger skirt system with the purpose of understanding the skirt's effect on the vehicle heave dynamics. Throughout the course of this work, the pure heave motion of a two dimensional section of the skirt is investigated using several mathematical models. Both the nonlinear and linearized analyses include a detailed model of the skirt geometry, which is modelled as a combination of inelastic membranes and links. Air flow processes from the bag to the cushion and from the cushion to the atmosphere are assumed to be quasisteady, and the bag and cushion volumes are modelled as lumped pneumatic capacitances. The modulation of the escaping cushion air by skirt-ground contact is also included. The nonlinear simulations reveal that characteristically nonlinear dynamical phenomena such as period doubling and chaos can be expected to occur during the normal operation of ACVs. Furthermore, a configuration representative of a 37 tonne vehicle shows a resonance at frequencies in the range for which humans are most sensitive. Although these results thus show that some aspects of the bag and finger skirt heave dynamics can be highly nonlinear, they indicate that under certain circumstances, standard linear techniques can yield useful insights. Results from the linear analysis suggest that changes in skirt geometry cannot be used to radically modify the undesirable heave response of the bag and finger skirt, but reducing the skirt mass is quite effective. The pneumatic capacitance of the bag and cushion volume proves to be an important factor in the heave response. In particular, it contributes to heave instability. The air compressibility also affects heave response at high frequencies, with the effect becoming more prominent as the flow rate is reduced. The importance of unsteady fan effects on ACV dynamics is investigated by the

  18. An experimental and theoretical investigation on the optical and photocatalytic properties of ZnS nanoparticles (United States)

    La Porta, F. A.; Nogueira, A. E.; Gracia, Lourdes; Pereira, W. S.; Botelho, G.; Mulinari, T. A.; Andrés, Juan; Longo, E.


    From the viewpoints of materials chemistry and physical chemistry, crystal structure directly determines the electronic structure and furthermore their optical and photocatalytic properties. Zinc sulfide (ZnS) nanoparticles (NPs) with tunable photoluminescence (PL) emission and high photocatalytic activity have been obtained by means of a microwave-assisted solvothermal (MAS) method using different precursors (i.e., zinc nitrate (ZN), zinc chloride (ZC), or zinc acetate (ZA)). The morphologies, optical properties, and electronic structures of the as-synthesized ZnS NPs were characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET) isotherms for N2 adsorption/desorption processes, diffuse reflectance spectroscopy (DRS), PL measurements and theoretical calculations. Density functional theory calculations were used to determine the geometries and electronic properties of bulk wurtzite (WZ) ZnS NPs and their (0001), (101 ̅0), (112 ̅0), (101 ̅1), and (101 ̅2) surfaces. The dependence of the PL emission behavior of ZnS NPs on the precursor was elucidated by examining the energy band structure and density of states. The method for degradation of Rhodamine B (RhB) was used as a probe reaction to investigate the photocatalytic activity of the as-Synthesised ZnS NPs under UV light irradiation. The PL behavior as well as photocatalytic activities of ZnS NPs were attributed to specific features of the structural and electronic structures. Increased photocatalytic degradation was observed for samples synthesized using different precursors in the following order: ZA

  19. Does Prop-2-ynylideneamine, HC≡CCH=NH, Exist in Space? A Theoretical and Computational Investigation

    Directory of Open Access Journals (Sweden)

    Osman I. Osman


    Full Text Available MP2, DFT and CCSD methods with 6-311++G** and aug-cc-pvdz basis sets have been used to probe the structural changes and relative energies of E-prop-2-ynylideneamine (I, Z-prop-2-ynylideneamine (II, prop-1,2-diene-1-imine (III and vinyl cyanide (IV. The energy near-equivalence and provenance of preference of isomers and tautomers were investigated by NBO calculations using HF and B3LYP methods with 6-311++G** and aug-cc-pvdz basis sets. All substrates have Cs symmetry. The optimized geometries were found to be mainly theoretical method dependent. All elected levels of theory have computed I/II total energy of isomerization (ΔE of 1.707 to 3.707 kJ/mol in favour of II at 298.15 K. MP2 and CCSD methods have indicated clearly the preference of II over III; while the B3LYP functional predicted nearly similar total energies. All tested levels of theory yielded a global II/IV tautomerization total energy (ΔE of 137.3–148.4 kJ/mol in support of IV at 298.15 K. The negative values of ΔS indicated that IV is favoured at low temperature. At high temperature, a reverse tautomerization becomes spontaneous and II is preferred. The existence of II in space was debated through the interpretation and analysis of the thermodynamic and kinetic studies of this tautomerization reaction and the presence of similar compounds in the Interstellar Medium (ISM.

  20. PUBLISHER'S NOTE: Microfabrication by localized electrochemical deposition: experimental investigation and theoretical modelling (United States)

    Said, R. A.


    During 2003, Dr R A Said published essentially duplicate versions of a paper in two archival journals: Nanotechnology and the Journal of The Electrochemical Society. The papers in question were: `Microfabrication by localized electrochemical deposition: experimental investigation and theoretical modelling' (2003 Nanotechnology 14 523) and `Shape formation of microstructures fabricated by localized electrochemical deposition' (2003 J. Electrochem. Soc. 150 C549). The two papers were submitted, revised, and published at essentially the same time. The papers used the same figures and neither paper referenced the other. Nanotechnology requires a signed copyright-transfer form assigning copyright in articles published to Institute of Physics Publishing, and the Journal of The Electrochemical Society requires the same for The Electrochemical Society. It is a tradition of long standing, stated in the information for contributors, that submission implies that the work has not been submitted, copyrighted, or accepted for publication elsewhere. Hence, duplicate publication not only raises legal questions and represents a serious breach of scientific ethics, but also leads to an unnecessary imposition on readers', referees', and editors' time. We regard this infraction as a serious matter. An apology from the author for this grave error is printed below. Author's apology I have mistakenly published similar results in two manuscripts in Nanotechnology and in the Journal of The Electrochemical Society, as stated above. I am responsible for this error. I agree with the Editors that such a practice should not have occurred, and I would like to sincerely apologize to Nanotechnology and the Journal of The Electrochemical Society, their publishers, and their readers for this matter. I will take actions in the future to prevent the occurrence of similar incidents. R A Said

  1. Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten. (United States)

    Arifin, Khuzaimah; Minggu, Lorna Jeffery; Daud, Wan Ramli Wan; Yamin, Bohari M; Daik, Rusli; Kassim, Mohammad B


    A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2-hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten with the molecular formula of C54H54O12S6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a=12.756(2) Å, b=21.560(3) Å, c=24.980(4) Å and β=103.998(3)°. Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.

  2. Experimental and theoretical investigations of the adhesion time of Penicillium spores to cedar wood surface

    Energy Technology Data Exchange (ETDEWEB)

    Soumya, Elabed [Laboratoire de Biotechnologie Microbienne, Faculté des Sciences et Techniques de Fès-Saïs (Morocco); Université Sidi Mohamed Ben Abdellah, Centre Universitaire Régional d' Interface-Fès (Morocco); Saad, Ibnsouda Koraichi, E-mail: [Laboratoire de Biotechnologie Microbienne, Faculté des Sciences et Techniques de Fès-Saïs (Morocco); Université Sidi Mohamed Ben Abdellah, Centre Universitaire Régional d' Interface-Fès (Morocco); Abdellah, Houari [Laboratoire de Biotechnologie Microbienne, Faculté des Sciences et Techniques de Fès-Saïs (Morocco); Hassan, Latrache [Laboratoire de Valorisation et de Sécurité des Produits Agroalimentaires, Faculté des Sciences et Techniques de Beni Mellal (Morocco)


    In this study, the adhesion of 4 Penicillium strains (Penicillium granulatum, Penicillium crustosum, Penicillium commune and Penicillium chrysogenum) on cedar wood was examined qualitatively and quantitatively by using the extended DLVO (XDLVO) approach and the environmental scanning electronic microscopy (ESEM) technique. A comparison between the XDLVO theories and the ESEM technique was also investigated. The adhesion tests revealed that P. chrysogenum was not able to adhere on the cedar wood substrata, as predicted by the XDLVO approach. We have also found by ESEM that the three Penicillium strains (P. granulatum, P. crustosum, P. commune) adhered on wood, as not predicted theoretically. Moreover, the time of adhesion (3 h and 24 h) was used not only to compare the capacity of adhesion according to contact time but also to explain the discrepancies between the XDLVO approach prediction and the adhesion experiments. A positive relationship between the XDLVO approach and adhesion experiments has been observed after 3 h of adhesion. In contrast, a contradiction between the XDLVO predictions and the adhesion test results has been noted after 24 h of adhesion of Penicillium strains to the wood surface. Highlights: ► Calculation of free energy of adhesion to cedar wood of Penicillium by XDLVO approach ► Adhesion is not favorable for all Penicillium spores–cedar wood combinations. ► Adhesion tests demonstrated the ability of Penicillium spores to adhere to cedar wood. ► XDLVO approach correlated well with the results obtained after 3 h of adhesion. ► Discrepancy between XDLVO predictions and experimental observations at 24 h of adhesion.

  3. The theoretical and experimental investigation of cosmic ray Forbush-effects (United States)

    Alania, M. V.; Bakradze, T. S.; Borchorishvili, T.; Bochikashvili, D. P.; Despotashvili, M. A.; Nachkebia, N. A.


    The theoretical results of analysis of the expected spatial distributions of density, gradients and anisotropy of cosmic rays, obtained on the basis of the numerical solution of anisotropic diffusion equation in the presence of the disturbances of shock wave type in the interplanetary space are presented. The theoretical calculations on the definition of the energy spectrum and anisotropy of galactic cosmic rays during Forbush effect are compared with the experimental data.

  4. Experimental and theoretical investigations of radial microwave integrated circuits with multi-semiconductor devices (United States)

    Derycke, A. C.; Dejaeger, M.; Salmer, G.; Debouard, A.

    A theoretical and experimental study of eccentered radial pretuned modules is presented. The modules can be used with several active devices to make power oscillator modules in millimeter waves, or to make VCO modules. The model makes possible the calculation of load impedance by considering the particular mode spectrum of radial circuits. The theoretical model is sufficiently accurate to estimate the load impedance variation versus frequency and its dependence on geometrical dimensions.

  5. Investigation, comparison and design of chambers used in centrifugal partition chromatography on the basis of flow pattern and separation experiments. (United States)

    Schwienheer, C; Merz, J; Schembecker, G


    In centrifugal partition chromatography (CPC) the separation efficiency is mainly influenced by the hydrodynamic of mobile and stationary phase in the chambers. Thus, the hydrodynamic has to be investigated and understood in order to enhance a CPC separation run. Different chamber geometries have been developed in the past and the influence of several phase systems and CPC operating conditions were investigated for these chambers. However, a direct comparison between the different chamber types has not been performed yet. In order to investigate the direct influence of the chamber design on the hydrodynamic, several chamber designs - partially similar in geometry to commercial available designs - are investigated under standardized conditions in the present study. The results show the influence of geometrical aspects of the chamber design on the hydrodynamic and therewith, on the separation efficiency. As a conclusion of the present study, some ideas for an optimal chamber design for laboratory and industrial purpose are proposed.

  6. Muramic Acid Measurements for Bacterial Investigations in Marine Environments by High-Pressure Liquid Chromatography (United States)

    Mimura, Toru; Romano, Jean-Claude


    Muramic acid, a constituent of procaryotic cell walls, was assayed by high-pressure liquid chromatography in samples from several marine environments (water column, surface microlayer, and sediment) and a bacterial culture. It is used as a microbial biomass indicator. The method gave a good separation of muramic acid from interfering compounds with satisfactory reproducibility. A pseudomonad culture had a muramic acid content of 4.7 × 10−10 to 5.3 × 10−10 μg per cell during growth. In natural water samples, highly significant relationships were found between muramic acid concentrations and bacterial numbers for populations of 108 to 1011 cells per liter. The muramic acid content in natural marine water decreased from 5.3 × 10−10 to 1.6 × 10−10 μg per cell with increasing depth. In coastal sediments exposed to sewage pollution, concentrations of muramic acid, ATP, organic carbon, and total amino acids displayed a parallel decrease with increasing distance from the sewage outlet. Advantages of muramic acid measurement by high-pressure liquid chromatography are its high sensitivity and reduction of preparation steps, allowing a short time analysis. PMID:16346848

  7. Investigation of wetted particle collisions theoretically and experimentally using a pendulum apparatus (United States)

    Donahue, Carly Michelle

    The addition of a small amount of liquid to a granular system can dramatically change the flow dynamics including the flowability, tensile strength, and segregation. Such liquid-coated particles coated are common in nature (e.g. avalanches, pollen capture) and in industry (e.g. granulation, particle filtration). Despite their ubiquity, predicting macro-scale (bulk) flows of liquid-coated particles is still elusive. A microscale (particle-level) investigation of the interactions of few wetted particles will lead to the identification of the dominant physical mechanisms which feeds into the understanding and modeling of bulk flows of wetted systems. Previous micro-scale studies of wetted particles have included experimental and theoretical efforts to study particle-wall collisions (both oblique and head-on) and particle-particle collisions (head-on only). Before using such micro-scale models to describe macro-scale flows, more general cases need to be first considered such as collisions between more than two particles and the rotational motion of agglomerates. The goal of this work is to address these two issues through a combination of experiments using a pendulum apparatus and theory. To investigate collisions between more than two particles, this work focuses on the normal (head-on) collision of three spheres. The foundation for such work is provided by first investigating analogous dry (non-wetted) systems. Experimental results are compared to soft-sphere models, which simultaneously account for all collisions, and a hard-sphere model, which treats the three-body collision as a series of two-body collisions. While the soft-sphere models generally predicts the post-collisional velocities better, the hard-sphere model exhibits a good comparison overall. In the wetted three-particle collisions, the pendulum apparatus is coined Stokes's cradle for the Stokes flow in the liquid gap between the particles. In two-body collisions, only two outcomes exist, namely stick

  8. The impact on CT dose of the variability in tube current modulation technology: a theoretical investigation (United States)

    Li, Xiang; Segars, W. Paul; Samei, Ehsan


    Body CT scans are routinely performed using tube-current-modulation (TCM) technology. There is notable variability across CT manufacturers in terms of how TCM technology is implemented. Some manufacturers aim to provide uniform image noise across body regions and patient sizes, whereas others aim to provide lower noise for smaller patients. The purpose of this study was to conduct a theoretical investigation to understand how manufacturer-dependent TCM scheme affects organ dose, and to develop a generic approach for assessing organ dose across TCM schemes. The adult reference female extended cardiac-torso (XCAT) phantom was used for this study. A ray-tracing method was developed to calculate the attenuation of the phantom for a given projection angle based on phantom anatomy, CT system geometry, x-ray energy spectrum, and bowtie filter filtration. The tube current (mA) for a given projection angle was then calculated as a log-linear function of the attenuation along that projection. The slope of this function, termed modulation control strength, α, was varied from 0 to 1 to emulate the variability in TCM technology. Using a validated Monte Carlo program, organ dose was simulated for five α values (α = 0, 0.25, 0.5, 0.75, and 1) in the absence and presence of a realistic system mA limit. Organ dose was further normalized by volume-weighted CT dose index (CTDIvol) to obtain conversion factors (h factors) that are relatively independent of system specifics and scan parameters. For both chest and abdomen-pelvis scans and for 24 radiosensitive organs, organ dose conversion factors varied with α, following second-order polynomial equations. This result suggested the need for α-specific organ dose conversion factors (i.e., conversion factors specific to the modulation scheme used). On the other hand, across the full range of α values, organ dose in a TCM scan could be derived from the conversion factors established for a fixed-mA scan (hFIXED). This was possible by

  9. Investigation into the temporal stability of aqueous standard solutions of psilocin and psilocybin using high performance liquid chromatography. (United States)

    Anastos, N; Barnett, N W; Pfeffer, F M; Lewis, S W


    This paper reports an investigation into the temporal stability of aqueous solutions of psilocin and psilocybin reference drug standards over a period of fourteen days. This study was performed using high performance liquid chromatography utilising a (95:5% v/v) methanol: 10 mM ammonium formate, pH 3.5 mobile phase and absorption detection at 269 nm. It was found that the exclusion of light significantly prolonged the useful life of standards, with aqueous solutions of both psilocin and psilocybin being stable over a period of seven days.

  10. Theoretical investigation of the optical and EPR parameters for VO 2+ion in some complexes (United States)

    Kalfaoğlu, Emel; Karabulut, Bünyamin


    The molecular orbital coefficients and the EPR parameters of trisodium citrate dihydrate, sodium hydrogen oxalate monohydrate, potassium d-gluconate monohydrate and L-Alanine vanadyl complexes are calculated theoretically. Two d-d transition spectra and EPR parameters for the VO2+ complex are calculated theoretically by using crystal-field theory. The calculated g and A paramaters have indicated that paramagnetic center is axially symmetric. Having the relations of g∥A⊥ for VO2+ ions, it can be concluded that VO2+ ions are located in distorted octahedral sites (C4v) elongated along the z-axis and the ground state of the paramagnetic electron is dxy.


    Institute of Scientific and Technical Information of China (English)

    DONG Zhi-yong; WU Chi-gong; YANG YONG-quan


    This paper presents entrainment mechanism,and transported and diffusion characteristics at the point of entry of submerged jet. The profiles of both velocity and concentration within the air-water mixing layer were theoretically deduced. And the comparisons between theoretical values and measured data were made. Results show that the velocity profile within the air-water mixing layer exhibits a form of error function. The concentrations of air entrainment in the internal and external regions of air-water mixing layer correspond to Gaussian distribution.

  12. ORAL ISSUE OF THE JOURNAL "USPEKHI FIZICHESKIKH NAUK": Theoretical investigations of the ferroelectric transition (United States)

    Maksimov, Evgenii G.


    The paper presents a historical review of theoretical concepts regarding the nature of the ferroelectric transition in crystals with a perovskite structure. We discuss Ginzburg's phenomenological theory, including the idea of the soft phonon mode as a reason for the ferroelectric transition. The role played by the dipole-dipole interaction in softening the optical phonon mode is considered in the framework of the theory of lattice dynamics. The experimental data and theoretical results are presented that prove that the ferroelectric transition in perovskite crystals is due to the soft mode and is a displacement-type transition.

  13. Applying 'Sequential Windowed Acquisition of All Theoretical Fragment Ion Mass Spectra' (SWATH) for systematic toxicological analysis with liquid chromatography-high-resolution tandem mass spectrometry. (United States)

    Arnhard, Kathrin; Gottschall, Anna; Pitterl, Florian; Oberacher, Herbert


    Liquid chromatography-tandem mass spectrometry (LC-MS/MS) has become an indispensable analytical technique in clinical and forensic toxicology for detection and identification of potentially toxic or harmful compounds. Particularly, non-target LC-MS/MS assays enable extensive and universal screening requested in systematic toxicological analysis. An integral part of the identification process is the generation of information-rich product ion spectra which can be searched against libraries of reference mass spectra. Usually, 'data-dependent acquisition' (DDA) strategies are applied for automated data acquisition. In this study, the 'data-independent acquisition' (DIA) method 'Sequential Windowed Acquisition of All Theoretical Fragment Ion Mass Spectra' (SWATH) was combined with LC-MS/MS on a quadrupole-quadrupole-time-of-flight (QqTOF) instrument for acquiring informative high-resolution tandem mass spectra. SWATH performs data-independent fragmentation of all precursor ions entering the mass spectrometer in 21m/z isolation windows. The whole m/z range of interest is covered by continuous stepping of the isolation window. This allows numerous repeat analyses of each window during the elution of a single chromatographic peak and results in a complete fragment ion map of the sample. Compounds and samples typically encountered in forensic casework were used to assess performance characteristics of LC-MS/MS with SWATH. Our experiments clearly revealed that SWATH is a sensitive and specific identification technique. SWATH is capable of identifying more compounds at lower concentration levels than DDA does. The dynamic range of SWATH was estimated to be three orders of magnitude. Furthermore, the >600,000 SWATH spectra matched led to only 408 incorrect calls (false positive rate = 0.06 %). Deconvolution of generated ion maps was found to be essential for unravelling the full identification power of LC-MS/MS with SWATH. With the available software, however, only semi

  14. Ultrafast Gain Dynamics in Quantum Dot Amplifiers: Theoretical Analysis and Experimental Investigations

    DEFF Research Database (Denmark)

    Poel, Mike van der; Gehrig, Edeltraud; Hess, Ortwin;


    Ultrafast gain dynamics in an optical amplifier with an active layer of self-organized quantum dots (QDs) emitting near 1.3$muhbox m$is characterized experimentally in a pump-probe experiment and modeled theoretically on the basis of QD Maxwell–Bloch equations. Experiment and theory are in good...

  15. First-Year Biology Students' Understandings of Meiosis: An Investigation Using a Structural Theoretical Framework (United States)

    Quinn, Frances; Pegg, John; Panizzon, Debra


    Meiosis is a biological concept that is both complex and important for students to learn. This study aims to explore first-year biology students' explanations of the process of meiosis, using an explicit theoretical framework provided by the Structure of the Observed Learning Outcome (SOLO) model. The research was based on responses of 334…

  16. Theoretical and experimental investigation of a waveguide CO2 laser with radio-frequency excitation

    NARCIS (Netherlands)

    Ilukhin, B.I.; Udalov, Yu.B.; Kochetov, I.V.; Ochkin, V.N.; Heeman-Ilieva, M.B.; Peters, P.J.M.; Witteman, W.J.


    A comprehensive experimental and theoretical study of the optimization of a continuous-wave radiofrequency (rf) excited CO2 waveguide laser is presented. The numerical simulation includes the modelling of the gas-discharge plasma parameters like the plasma impedance and energy deposition, the laser

  17. Investigating the Theoretical Structure of the Stanford-Binet-Fifth Edition (United States)

    DiStefano, Christine; Dombrowski, Stefan C.


    The fifth edition of the Stanford-Binet test went through significant reformulation of its item content, administration format, standardization procedures, and theoretical structure. Additionally, the test was revised to measure five factors important to intelligence across both verbal and nonverbal domains. To better understand these substantial…


    Directory of Open Access Journals (Sweden)

    Игорь Михайлович Гаранжа


    Full Text Available We have completed some theoretical investigations of deformation mode of lattice intermediate supports with suspended insulating garlands with further experimental verification of the results. The necessity of accounting the dynamic component of the emergency load for the design, review and reconstruction of overhead power lines has been substantiated.

  19. Discrimination of eight chloramphenicol isomers by liquid chromatography tandem mass spectrometry in order to investigate the natural occurence of chloramphenicol

    NARCIS (Netherlands)

    Berendsen, B.J.A.; Zuidema, T.; Jong, de J.; Stolker, A.A.M.; Nielen, M.W.F.


    This paper describes the discrimination of eight different isomers of chloramphenicol (CAP), an antibiotic banned for use in food producing animals, by reversed phase and chiral liquid chromatography in combination with tandem mass spectrometric detection. Previously, by liquid chromatography couple

  20. Theoretical investigation of formation of impurity bipolaronic states in covalent semiconductors and high temperature superconductors

    CERN Document Server

    Yavidov, B Y


    superconducting properties of doped HTSC compounds have been accounted for with framework of lattice and impurity bipolarons concepts. The theoretical results obtained are in satisfactory agreement with experiment. A theory has been developed of carrier localization around an impurity which takes account of correlation effect between carriers, short- and long range interaction in 'carrier-impurity-lattice' system within the framework of the continuum model in the adiabatic approximation. Possibility of impurity (bi)polaron formation in covalent semiconductors (Si) and high temperature superconductors (HTSC) (La sub 2 sub - sub x Sr sub x Cu sub 4) has been studied theoretically. The impurity bi polaron formation has been analyzed by two scenarios: paring and sequential localization of carriers in the vicinity of impurity atom. It is shown that the impurity bi polaron of large radius does not form in Si while its formation is possible in crystals with x<0.186, where x is the ratio of high frequency dielectr...

  1. Unsteady flow and vibrations induced in turbine blades: Contributions to theoretical and experimental investigations

    Energy Technology Data Exchange (ETDEWEB)

    Benvenuto, G.; Troilo, M. (L' Aquila Univ. (Italy); Genoa Univ. (Italy))


    A mathematical model is developed for fluid dynamic auto-excitated vibrations in turbine blades. In particular, with reference to theoretical aspects, the paper deals with the numerical analytical methods developed for the prediction of flutter instability in turbine cascades. With reference to experimental aspects, a description is given of recently installed instrumentation (at the test facility of the University of Genoa, Italy) for flow visualization and detection of unsteady flows by means of interferometry.

  2. (Original article) Investigation of structure and composition of executive functions: analysis of theoretical models


    Dias, Natália Martins; Gomes,Cristiano Mauro Assis; Reppold, Caroline Tozzi; Fioravanti-Bastos, Ana Carolina; Pires,Emmy Uehara; Carreiro, Luiz Renato Rodrigues; SEABRA,Alessandra Gotuzo


    Despite relative consensus on the existence of three basic executive functions (EF) (inhibition, working memory and cognitive flexibility) there is narrower knowledge on its organization and contribution to task solution. The study tested different theoretical models about the structure and composition of EF. The correlation matrix of Miyake et al. (2000), which evaluated university students in a set of 15 EF tasks, was adopted. Model 1 displays a general factor and specific components. In mo...

  3. Investigation of the interfacial tension of complex coacervates using field-theoretic simulations (United States)

    Riggleman, Robert A.; Kumar, Rajeev; Fredrickson, Glenn H.


    Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field-theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.

  4. Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Rajeev [ORNL


    Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.

  5. Theoretical analysis and experimental investigation of valveless piezoelectric pump with unsymmetrical ridges

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jianhui; LU Jizhuang; XIA Qixiao; LI Hong


    A novel valveless piezoelectric pump with unsymmetrical ridges is presented at first. It ingeniously uti- lizes the inner space of its chamber by developing its chamber bottom into unsymmetrical ridges along the direction of the inlet and outlet of the pump. Hence, a series of cuneiform channels are asymmetrically and alternately formed between the unsymmetrical ridges and the piezoelectric vibrator, which enables the pump to form a one-way flow instead of the func- tion of the traditional diffuse or nozzle elements fitted outside the chamber. Then, by analyzing the vibration of the piezo- electric vibrator, the vibration deformation function and the equation of volume change are established. Meanwhile, the theoretical equation of the pump flow rate is established. Finally, a real valveless piezoelectric pump with unsymmetri- cal ridges is manufactured, and the flow rate of the pump is measured through experiments. It is proved that the theory is rational and correct by comparing the experimental flow rate and the theoretical flow rate. In addition, for calculating the theoretical flow rate, the positive and converse flow resis- tance coefficients of unsymmetrical ridges are measured through experiments, when one slope angle of the unsym- metrical ridges is 90° and another is changing from 20° to 60°, respectively.

  6. A numerical investigation into the solids phase chromatography using a combined continuous and discrete approach

    Institute of Scientific and Technical Information of China (English)


    Solids phase chromatography for particle classification is based on different retention times of particles with different properties when they are elutriated through a confined geometry.This work aims at a fundamental understanding of such a technology by using the combined continuous and discrete method.A packed bed is employed as the model confined geometry.The numerical method is compared first with experimental observations,followed by a parametric analysis of the effects on the flow hydrodynamics and solids behaviour of various parameters including the number of injected particles,the superficial gas velocity,the contact stiffness and the diameter ratio of the packed column to the packed particles.The results show that the modelling captures some important features of the flow of an injected pulse of fine particles in a packed bed. An increase in the number of injected particles or the superficial gas velocity reduces the retention time,whereas the contact stiffness does not show much effect over the range of 5×102 to5×104 N/m.It is also found that the effect on the retention time of the diameter ratio of the packed column to the packed particles seems complex showing a non-monotonous dependence.

  7. Investigation of olopatadine hydrochloride under stress conditions by hydrophilic interaction liquid chromatography

    Directory of Open Access Journals (Sweden)

    Maksić Jelena Đ.


    Full Text Available The purpose of the present research was to conduct stress degradation studies on the olopatadine hydrochloride, an antiallergic drug, using the hydrophilic interaction liquid chromatography (HILIC. HILIC requires the utilization of polar and moderately polar stationary phases and aqueous-organic mobile phase usually containing more than 70% of organic solvent. In this study, olopatadine hydrochloride was subjected to acid and base hydrolysis, oxidation and termolytic degradation in order to estimate its stability under different stress conditions recommended by ICHQ1A (R2 guideline. Degree of degradation was followed by HILIC method. The chromatographic conditions were: column Betasil Cyano (100 mm × 4.6 mm, 5 mm particle size, mobile phase consisted of acetonitrile and ammonium acetate 5 mM (pH adjusted to 4.50 in ratio 85:15 V/V, flow rate was 1 mL min-1, column temperature was set at 30°C and detection was performed at 257 nm. Results obtained for stress studies indicated that olopatadine hydrochloride underwent transformation under acidic and oxidative (30% w/v hydrogen peroxyde conditions showing high degree of degradation. Furthermore, it was found that olopatadine hydrochloride is relatively stable when exposed to thermal (60°C and basic (1 M NaOH conditions. Therewith, kinetics of degradation reaction was determined with an aim to define the corresponding reaction rate constants and half-lives. Firstly, the order of the reaction was evaluated experimentally using the integral method. Based on the calculated values of the correlation coefficients, it was shown that the acidic, basic and oxidative degradation are the second-order reaction. High stability under basic conditions was achieved on the basis of the great degradation half-life values. Also, it has been verified that acidic degradation is the fastest reaction. [Projekat Ministarstva nauke Republike Srbije, br. 172052

  8. Investigation of isovaline enantiomeric excesses in CM meteorites using liquid chromatography time of flight mass spectrometry (United States)

    Glavin, Daniel P.; Dworkin, Jason P.


    The enantiomeric abundances of the alpha-dialkyl amino acid isovaline were measured in the CM2 meteorites Murchison and LEW 90500 using a new liquid chromatography-time of flight-mass spectrometry (LC-ToF-MS) technique coupled with OPA/NAC derivatization and UV fluorescence detection. Previous analyses of Murchison have shown that L-enantiomeric excesses of isovaline range from 0 to 15.2% with significant variation between meteorite fragments [1]. For this study, hot water extracts of interior fragments (> 2 cm from fusion crust) of the Murchison (USNM 6650.2, mass 6 g) and LEW 90500 (split 69, parent 1, mass 5 g) carbonaceous meteorites were analyzed. Enantiomeric excesses were measured using the single ion LC-ToF-MS trace for the OPA/NAC derivative of isovaline at d z 393.15 (Fig. 1). L-isovaline excesses in these meteorite samples ranged from 18.9 to 20.5% for Murchison and -0.5 to 3.0% for LEW 90500. The measured values for Murchison are the largest enantiomeric excesses for isovaline reported to date. The enantiomeric excesses of L-isovaline cannot be the result of interference from other C5 amino acid isomers present in the meteorites or terrestrial contamination from the landing site environments. The L-isovaline excesses in Murchison are inconsistent with the synthesis of all of the isovaline by the Strecker-cyanohydrin pathway on the CM meteorite parent body. The mechanism(s) for the formation of the enantiomeric asymmetry in isovaline in Murchison are currently unknown and it is not clear how the asymmetry of alpha-dialkyl amino acids could be transferred to the a-hydrogen protein amino acids common in all life on Earth today.

  9. Energy levels and quantum states of [Leu]enkephalin conformations based on theoretical and experimental investigations

    DEFF Research Database (Denmark)

    Abdali, Salim; Jensen, Morten Østergaard; Bohr, Henrik


    This paper describes a theoretical and experimental study of [Leu]enkephalin conformations with respect to the quantum estates of the atomic structure of the peptide. Results from vibrational absorption measurements and quantum calculations are used to outline a quantum picture and to assign...... vibrational modes to the different conformations. The energy landscape of the conformations is reported as a function of a Hamming distance in Ramachandran space. Molecular dynamics simulations reveal a pronounced stability of the so-called single-bend low-energy conformation, which supports the derived...... quantum picture of this peptide....

  10. Theoretical Investigation of Laser-Radiation Effects on Satellite Solar Cells (United States)

    Abdel-Hadi, Yasser; El-Hameed, Afaf; Hamdy, Ola

    This research concerns with the studying of laser-powered solar panels for space applications. A model describing the laser effects on satellite solar cell has been developed. These effects are studied theoretically in order to determine the performance limits of the solar cells when they are powered by laser radiation during the satellite eclipse. A comparison between some different common types of the solar cells used for these purpose is considered in this study. The obtained results are reported to optimize the use of laser-powered satellites.

  11. Theoretical investigation on structural and electronic properties of PdO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Viswanathan, E.; Sundareswari, M., E-mail:, E-mail:; Jayalakshmi, D. S.; Manjula, M. [Department of Physics, Sathyabama University, Jeppiaar Nagar, OMR, Chennai-600119 (India)


    Theoretical studies on rutile type Palladium Dioxide were carried out with the aim of analyzing structural and electronic properties at ambient condition using the first principle calculation based on density functional theory. Within the framework of density functional theory, we used full potential linearized augmented plane wave method(FP-LAPW) in Wien 2k code. The exchange and correlation effect is treated with generalized gradient approximation (GGA) using the Perdew, Burke and Eruzeroff form. The charge density plots, density of states and band structure are plotted and discussed.

  12. Application of spectral deconvolution and inverse mechanistic modelling as a tool for root cause investigation in protein chromatography. (United States)

    Brestrich, Nina; Hahn, Tobias; Hubbuch, Jürgen


    In chromatographic protein purification, process variations, aging of columns, or processing errors can lead to deviations of the expected elution behavior of product and contaminants and can result in a decreased pool purity or yield. A different elution behavior of all or several involved species leads to a deviating chromatogram. The causes for deviations are however hard to identify by visual inspection and complicate the correction of a problem in the next cycle or batch. To overcome this issue, a tool for root cause investigation in protein chromatography was developed. The tool combines a spectral deconvolution with inverse mechanistic modelling. Mid-UV spectral data and Partial Least Squares Regression were first applied to deconvolute peaks to obtain the individual elution profiles of co-eluting proteins. The individual elution profiles were subsequently used to identify errors in process parameters by curve fitting to a mechanistic chromatography model. The functionality of the tool for root cause investigation was successfully demonstrated in a model protein study with lysozyme, cytochrome c, and ribonuclease A. Deviating chromatograms were generated by deliberately caused errors in the process parameters flow rate and sodium-ion concentration in loading and elution buffer according to a design of experiments. The actual values of the three process parameters and, thus, the causes of the deviations were estimated with errors of less than 4.4%. Consequently, the established tool for root cause investigation is a valuable approach to rapidly identify process variations, aging of columns, or processing errors. This might help to minimize batch rejections or contribute to an increased productivity.

  13. Electronic structure of the diatomic VO anion: A combined photoelectron-imaging spectroscopic and theoretical investigation (United States)

    Cheng, Shi-Bo; Harmon, Christopher L.; Yang, Huan; Castleman, A. W.


    The electronic structure of the diatomic VO anion was explored by combining the photoelectron-imaging spectroscopy and high-level theoretical calculations. The electron affinity (EA) of VO is determined to be 1.244 ± 0.025 eV from the vibrationally resolved photoelectron spectrum acquired at 532 nm. The anisotropy parameter (β) for the EA defined peak is measured to be 1.59 ± 0.02, indicating that it is the 9σ electron attachment leading to the formation of the ground state of V O- . The present imaging experiment provides direct evidence that the ground state of V O- is X 3Σ- with a (3π ) 4(8σ ) 2(9σ ) 2(1δ ) 2 electron configuration, which resolves the significant discrepancy in previous experiment and theory. In addition, the molecular orbitals and bonding involved in the anionic VO cluster are also examined based on the present high-level theoretical calculations.

  14. An experimental and theoretical investigation of the C(1D) + D2 reaction

    CERN Document Server

    Hickson, Kevin M


    In a previous joint experimental and theoretical study of the barrierless chemical reaction C(1D) + H2 at low temperatures (300-50 K) [K. M. Hickson, J.-C. Loison, H. Guo, Y. V. Suleimanov, J. Phys. Chem. Lett., 2015, 6, 4194.], excellent agreement was found between experimental thermal rate constants and theoretical estimates based on ring polymer molecular dynamics (RPMD) over the two lowest singlet potential energy surfaces (PESs). Here, we extend this work to one of its deuterated counterparts, C(1D) + D2, over the same temperature range. Experimental and RPMD results are in very good agreement when contributions from both PESs to this chemical reaction are included in the RPMD simulations. The deviation between experiment and the RPMD calculations does not exceed 25 % and both results exhibit a slight negative temperature dependence. The first excited 1A" PES plays a more important role than the ground 1A' PES as the temperature is decreased, similar to our previous studies of the C(1D) + H2 reaction but...

  15. Theoretical and experimental investigation on optimization of a non-contact air conveyor

    Institute of Scientific and Technical Information of China (English)

    钟伟; 黎鑫; 陶国良; 路波; 香川利春


    Air film conveyors equipped with porous pads have been developed to bring the liquid crystal display (LCD) into a non-contact state during transportation process. In this work, a theoretical model including flow property of porous media and Reynolds equation is established within a representative region in order to optimize the design parameters of a partial porous air conveyor. With the theoretical model, an optimization method using nondominated sorting genetic algorithm – II (NSGA-II) is applied for a two-objective optimization to achieve a minimum air consumption and maximum load capacity. Three Pareto-optimal solutions are selected to analyze the influence of each parameter on the characteristics of the air conveyor, and the results indicate that the position of the porous pads has the most significant impact on the performance and of course must be determined with care. Furthermore, experimental results in terms of the supporting force versus gap clearance show that the optimized air conveyor can greatly improve the load capacity over the normal one, indicating that the optimization method is applicable for practical use.

  16. Theoretical Investigation of Dissolution Test Criteria for Waiver of Clinical Bioequivalence Study. (United States)

    Sugano, Kiyohiko


    The purpose of the present study was to provide a theoretical basis for the dissolution test criteria of a biowaiver scheme. The critical dissolution number (Dncrit) was defined as a value to show bioequivalence of AUC and Cmax against infinitely rapid dissolution (Dn = ∞). The gastrointestinal tract was represented by the one-compartment model. The dissolution of a drug was expressed by the Noyes-Whitney equation. The permeation of a drug was expressed by the first-order equation. The approximate analytical solutions of Dncrit were derived from the analytical solution for the fraction of a dose absorbed [Fa = 1 - exp(-1/(1/Dn + Do/Pn)]; Do, the dose number; Pn, the permeation number). Numerical integration was also performed to calculate Dncrit more accurately. Dncrit was found to become smaller as Pn and Do became smaller. Dncrit for Cmax was found to be dependent on the elimination half-life of a drug as well as Pn and Do. The Fa equation can be an appropriate theoretical basis for a biowaiver scheme.

  17. An experimental and theoretical investigation of the N + C2 reaction at low temperature

    CERN Document Server

    Loison, Jean-Christophe; Han, Shanyu; Hickson, Kevin M; Guo, Hua; Xie, Daiqian


    Rate constants for the N + C2 reaction have been measured in a continuous supersonic flow reactor over the range 57 K to 296 K by the relative rate technique employing the N + OH - H + NO reaction as a reference. Excess concentrations of atomic nitrogen were produced by the microwave discharge method and C2 and OH radicals were created by the in-situ pulsed laser photolysis of precursor molecules C2Br4 and H2O2 respectively. In parallel, quantum dynamics calculations were performed based on an accurate global potential energy surfaces for the three lowest lying quartet states of the C2N molecule. The 14A" potential energy surface is barrierless, having two deep potential wells corresponding to the NCC and CNC intermediates. Both the experimental and theoretical work show that the rate constant decreases to low temperature, although the experimentally measured values fall more rapidly than the theoretical ones except at the lowest temperatures. Astrochemical simulations indicate that this reaction could be the...

  18. Theoretical and experimental investigations on the dynamic and thermodynamic characteristics of the linear compressor for the pulse tube cryocooler (United States)

    Zhang, L.; Dang, H. Z.; Tan, J.; Bao, D.; Zhao, Y. B.; Qian, G. Z.


    Theoretical and experimental investigations on the dynamic and thermodynamic characteristics of a linear compressor incorporating the thermodynamic characteristics of the inertance tube pulse tube cold finger have been made. Both the compressor and cold finger are assumed as a one-dimensional thermodynamic model. The governing equations of the thermodynamic characteristics of the working gas are summarized, and the effects of the cooling performance on the working gas in the compression space are discussed. Based on the analysis of the working gas, the governing equations of the dynamic and thermodynamic characteristics of the compressor are deduced, and then the principles of achieving the optimal performance of the compressor are discussed in detail. Systematic experimental investigations are conducted on a developed moving-coil linear compressor which drives a pulse tube cold finger, which indicate the general agreement with the simulated results, and thus verify the rationality of the theoretical model and analyses.

  19. Theoretical investigation on the reaction of adhesion unit dopa in mussel with electrolyzing seawater. (United States)

    Chen, Shuang-Kou; Wang, Bo-Chu; Zhou, Tai-Gang; Feng, Ying-Zhu; Liang, Hua-Ming; Huang, Wen-Zhang


    Adhesive proteins secreted by the marine mussel could bind strongly to all kinds of surfaces, for instance, ship hulls and petroleum pipelines. Studies indicated that there was an unusual amino acid 3,4-dihydroxy-l-phenylanine (dopa), which was the crucial super adhesive unit in the proteins. The technology of electrolyzing seawater was employed to generate HOCl solution to hinder the adhesion. However, the detailed anti-fouling mechanism of HOCl solution remained unknown to be fully explained. Herein, we theoretically reported a study of single molecular (dopa) reaction under the HOCl solution environment, which would be helpful to reveal the anti-fouling mechanism through electrolyzing seawater. By using the density functional theory (DFT) quantum mechanics procedure, we theoretically studied the reaction mechanism of the adhesive unit dopa in mussel with electrolyzing seawater. Two possible pathways (1 and 2) were obtained (Fig. 6). The transition state for each pathway was determined, the intrinsic reaction coordinate (IRC) was analyzed and the mechanism had been confirmed. The calculations indicated dopa tended to have electrophonic attacking substitution reaction to generate 3-chlorine-4,5-dihydroxyphenylalanine (dopa-Cl) with different pathways, which hindered the formulation of conjuncted dopa-dopa and thus the stickiness among mussel adhesive proteins reduced. The transition states computation showed that pathway (1) had one transition state (TS1-1) with an activation energy of 102.22 kJ mol(-1), while pathway (2) had two transition states (TS2-1, TS2-2) with activation energies of 191.98 kJ mol(-1) and 42.00 kJ mol(-1) respectively and one intermediate (IM2-1). Rate constant value of pathway (1) was much bigger than that of pathway (2) regardless of high or low temperature, which meant that in the reaction process, pathway (1) was the favorable reaction step; but as the temperature rose, the competitiveness of pathway (2) gradually increased. After the

  20. Self-condensation of n-(N-propyl)butanimine: NMR and mass spectral analyses and investigation by theoretical calculation

    Energy Technology Data Exchange (ETDEWEB)

    Manfrini, Rozangela Magalhaes; Teixeira, Flavia Rodrigues; Pilo-Veloso, Dorila; Alcantara, Antonio Flavio de Carvalho, E-mail: [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Inst. de Ciencias Exatas. Dept. de Quimica; Nelson, David Lee [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Fac. de Farmacia. Dept. de Quimica; Siqueira, Ezequias Pessoa de [Centro de Pesquisas Rene Rachou (FIOCRUZ), Belo Horizonte, MG (Brazil)


    The stability of N-propylbutanimine (1) was investigated under different experimental conditions. The acid-catalyzed self-condensation that produced the E-enimine (4) and Z-inimine (5) was studied by experimental analyses and theoretical calculations. Since the calculations for the energy of 5 indicated that it had a lower energy than 4, yet 4 was the principal product, the self-condensation of 1 must be kinetically controlled. (author)

  1. Valence and lowest Rydberg electronic states of phenol investigated by synchrotron radiation and theoretical methods (United States)

    Limão-Vieira, P.; Duflot, D.; Ferreira da Silva, F.; Lange, E.; Jones, N. C.; Hoffmann, S. V.; Śmiałek, M. A.; Jones, D. B.; Brunger, M. J.


    We present the experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectra of phenol covering for the first time the full 4.3-10.8 eV energy-range, with absolute cross sections determined. Theoretical calculations on the vertical excitation energies and oscillator strengths were performed using time-dependent density functional theory and the equation-of-motion coupled cluster method restricted to single and double excitations level. These have been used in the assignment of valence and Rydberg transitions of the phenol molecule. The VUV spectrum reveals several new features not previously reported in the literature, with particular reference to the 6.401 eV transition, which is here assigned to the 3sσ/σ∗(OH)←3π(3a″) transition. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of phenol in the earth's atmosphere (0-50 km).

  2. Conformational and stereoeletronic investigations of muscarinic agonists of acetylcholine by NMR and theoretical calculations (United States)

    da Silva, Julio Cesar A.; Ducati, Lucas C.; Rittner, Roberto


    NMR solvent effects and theoretical calculations showed muscarinic agonists present a large stability for their near synclinal conformations, indicating the presence of significant stabilization factors. Analysis of the results clearly indicated that this stability is not determined by the dihedral around the substituted C-C ethane bond, as stated by some authors, but a consequence of the geometry adopted in order to maximize N+/O interactions in this type of molecules. It can be assumed that acetylcholine and its muscarinic agonists exhibit their biologic activity when the positively charged nitrogen and the oxygen atoms are in the same side of the molecule within an interatomic distance ranging from 3.0 to 6.0 Å.

  3. Experimental and theoretical investigations of the stereoselective synthesis of p-stereogenic phosphine oxides. (United States)

    Copey, Laurent; Jean-Gérard, Ludivine; Framery, Eric; Pilet, Guillaume; Robert, Vincent; Andrioletti, Bruno


    An efficient enantioselective strategy for the synthesis of variously substituted phosphine oxides has been developed, incorporating the use of (1S,2S)-2-aminocyclohexanol as the chiral auxiliary. The method relies on three key steps: 1) Highly diastereoselective formation of P(V) oxazaphospholidine, rationalized by a theoretical study; 2) highly diastereoselective ring-opening of the oxazaphospholidine oxide with organometallic reagents that takes place with inversion of configuration at the P atom; 3) enantioselective synthesis of phosphine oxides by cleavage of the remaining P-O bond. Interestingly, the use of a P(III) phosphine precursor afforded a P-epimer oxazaphospholidine. Hence, the two enantiomeric phosphine oxides can be synthesized starting from either a P(V) or a P(III) phosphine precursor, which constitutes a clear advantage for the stereoselective synthesis of sterically hindered phosphine oxides.

  4. Theoretical investigations of electron emission after water vapour ionization by light ion impact

    Energy Technology Data Exchange (ETDEWEB)

    Champion, C. [Laboratoire de Physique Moleculaire et des Collisions, ICPMB (FR2843), Institut de Physique, Universite Paul Verlaine-Metz, 1 Boulevard Arago, 57078 Metz Cedex 3 (France)], E-mail:; Dal Cappello, C. [Laboratoire de Physique Moleculaire et des Collisions, ICPMB (FR2843), Institut de Physique, Universite Paul Verlaine-Metz, 1 Boulevard Arago, 57078 Metz Cedex 3 (France)


    An ab initio quantum-mechanical treatment is applied for treating the ionization process of water vapour by light ions. In this theoretical model, the initial state of the system is composed of a projectile and a water target described by a plane wave and an accurate one-centre molecular wave function, respectively, whereas the final state is constituted by a slow ejected electron and a scattered projectile represented by a Coulomb wave and a plane wave, respectively. The obtained results are compared to available experimental data in terms of doubly differential cross sections (DDCS), singly differential cross sections (SDCS) and total cross sections (TCS). A good agreement is generally found especially for the SDCS and the TCS.

  5. An experimental and theoretical investigation into positron and electron scattering from formaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Zecca, A; Trainotti, E; Chiari, L [Department of Physics, University of Trento, Povo, I-38123 Trento (Italy); GarcIa, G [Instituto de Matematicas y Fisica Fundamental, CSIC, Serrano 121, 28006 Madrid (Spain); Blanco, F [Facultad de Ciencias Fisicas, Departamento de Fisica Atomica, Molecular y Nuclear, Universidad Complutense, Avda. Complutense s/n, E-28040 Madrid (Spain); Bettega, M H F [Departamento de Fisica, Universidade Federal do Parana, Caixa Postal 19044, 81531-990 Curitiba, Parana (Brazil); Varella, M T do N [Instituto de Fisica, Universidade de Sao Paulo, Caixa Postal 66318, 05315-970 Sao Paulo, SP (Brazil); Lima, M A P [Instituto de Fisica ' Gleb Wataghin' , Universidade Estadual de Campinas, Caixa Postal 6165, 13083-970 Campinas, Sao Paulo (Brazil); Laboratorio Nacional de Ciencia e Tecnologia do Bioetanol (CTBE), Centro Nacional de Pesquisa em Energia e Materiais (CNPEM), Caixa Postal 6170, 13083-970 Campinas, Sao Paulo (Brazil); Brunger, M J, E-mail: [ARC Centre for Antimatter-Matter Studies, School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, South Australia 5001 (Australia)


    We report on measurements of total cross sections (TCSs) for positron scattering from the fundamental organic molecule formaldehyde (CH{sub 2}O). The energy range of these measurements was 0.26-50.3 eV, whereas the energy resolution was {approx}260 meV. To assist us in interpreting these data, Schwinger multichannel level calculations for positron elastic scattering from CH{sub 2}O were also undertaken (0.5-50 eV). These calculations, incorporating an accurate model for the target polarization, are found to be in good qualitative agreement with our measured data. In addition, in order to compare the behaviour of positron and electron scattering from this species, independent atom model-screened additivity rule theoretical electron TCSs, now for energies in the range 1-10 000 eV, are also reported.

  6. Role of magnesium in ZnS structure: Experimental and theoretical investigation

    Directory of Open Access Journals (Sweden)

    M. Y. Shahid


    Full Text Available Wide band gap semiconductor materials are extending significant applications in electronics and optoelectronics industry. They are showing continued advancement in ultraviolet to infrared LEDs and laser diodes. Likewise the band gap tunability of ZnS with intentional impurities such as Mg and Mn are found useful for optoelectronic devices. Information from literature indicates slight blue shift in the band gap energy of ZnS by Mg doping but nevertheless, we report a reasonable red shift (3.48 eV/356 nm to 2.58 eV/480 nm in ZnS band gap energy in Mg-ZnS structure. Theoretical model based on first principle theory using local density approximation revealed consistent results on Mg-ZnS structure. Similarly, structural, morphological, optical and electrical properties of the as grown Mg-ZnS were studied by XRD, SEM, FTIR, EDS, UV-Vis Spectrophotometer and Hall measurement techniques.

  7. Theoretical and experimental investigation of a rectenna element for microwave power transmission (United States)

    Mcspadden, James O.; Yoo, Taewhan; Chang, Kai


    A microstrip measurement system has been designed to analyze packaged GaAs Schottky barrier diodes under small and large signal conditions. The nonlinear equivalent circuit parameters of the diode are determined using a small signal test method that analyzes the diode's scattering parameters at various bias levels. The experimental results of a 2.45 GHz diode are verified using a nonlinear circuit simulation program based on a multireflection algorithm. A 35 GHz rectenna has been built using a microstrip patch antenna and Ka-band mixer diode. The measured efficiency was 29 percent at 120 mW input power. A frequency selective surface is designed using an equivalent circuit model to reduce the second harmonic radiations for a 2.45 GHz rectenna. Theoretical results are found to be in fairly good agreement with experiments.

  8. Theoretical and experimental investigation of direct detection optical OFDM transmission using beat interference cancellation receiver. (United States)

    Nezamalhosseini, S Alireza; Chen, Lawrence R; Zhuge, Qunbi; Malekiha, Mahdi; Marvasti, Farokh; Plant, David V


    We theoretically and experimentally evaluate a beat interference cancellation receiver (BICR) for direct detection optical orthogonal frequency-division multiplexing (DD-OFDM) systems that improves the spectral efficiency (SE) by reducing the guard band between the optical carrier and the optical OFDM signal while mitigating the impact of signal-signal mixing interference (SSMI). Experimental results show that the bit-error-rate (BER) is improved by about three orders of magnitude compared to the conventional receiver after 320 km single-mode fiber (SMF) transmission for 10 Gb/s data with a 4-QAM modulation using reduced guard band single-sideband OFDM (RSSB-OFDM) signal with 1.67 bits/s/Hz SE.

  9. [Theoretical investigation on the structure and vibration spectrum of D-luciferin]. (United States)

    Zhu, Yuan-Qiang; Zhang, Li; Guo, Jian-Chun


    In the present study, the geometry of D-Luciferin was fully optimized by the density functional theory at the B3LYP/6-311++G** and B3PW91/6-311++G** level, and the Cartesian coordinate force constant was calculated at the same level. The scaled quantum mechanism force field (SQM) method was performed to analyze the vibration spectrum. The local internal symmetry coordinates were defined using the method given by Pulay. The theoretical force field matrix, which was obtained through molecular vibration calculation programs, was transformed from Cartesian coordinates into the local internal coordinates. A normal coordinate analysis was carried out using GF matrix method developed by Wilson to give the scaled vibration frequencies and the potential energy distributions (PEDs). In order to make the vibration frequencies in good agreement with the experimental values, we empirically scale the theoretical force fields. According to PEDs, all vibration modes were assigned reliably to certain vibration frequencies. The calculated results show that the D-Luciferin molecule belongs to the point group C1 and involves 66 free degrees of vibration. All vibration modes are infrared and Raman activity. In the Infrared spectrum, the vibration frequency of the strongest absorption peak is 1,780 cm(-1), and the absorption intensity is 507 KM · mol(-1), which is mainly contributed by the stretching vibration mode of the C21==O22, double bond with the PEDs of 93%. In the Raman spectrum, the vibration frequency in the range of 1,200-1.700 cm(-1) presented strong Raman activity, the frequency of the strongest absorption peak is 1,573 cm(-1), and the absorpiton intensity is 297 KM · mol, which is mainly contributed by the stretching vibration made of the C21==N22 double bond in the five-membered ring. The results are helpful to further studying the structure and the luminescence activity of Luciferin derivatives in experiment and theory.

  10. Experimental investigation of liquid chromatography columns by means of computed tomography

    DEFF Research Database (Denmark)

    Astrath, D.U.; Lottes, F.; Vu, Duc Thuong;


    dispersive model (EDM) and varying the so called apparent axial dispersion coefficient. The additivity of the first and second central moments was exploited to estimate column efficiency in different regions of the column. The results showed that the columns under investigation offered a higher column...

  11. Flow Field and Performance of Cross Flow Fans--Experimental and Theoretical Investigations

    Institute of Scientific and Technical Information of China (English)

    Martin Gabi; Simon Dornstetter; Toni Klemm


    Due to the construction and the operating principle the prediction of performance of Cross Flow Fans (CFF) is difficult and the knowledge about the internal flow regime is limited. To investigate the impact of geometrical parameters on the performance of CFF, experimental investigations, using Particle Imaging Velocimetry (PIV),and CFD calculations were carried out. Some results of PIV measurements and CFD calculations are presented,which give an impression of the internal flow and confirm the numerical calculations.

  12. An experimental and theoretical investigation into the ``worm-hole'' effect (United States)

    Zhao, Liang; Su, Jiancang; Zhang, Xibo; Pan, Yafeng; Wang, Limin; Fang, Jinpeng; Sun, Xu; Li, Rui; Zeng, Bo; Cheng, Jie


    On a nanosecond time scale, solid insulators abnormally fail in bulk rather than on surface, which is termed as the "worm-hole" effect. By using a generator with adjustable output pulse width and dozens of organic glass (PMMA) and polystyrene (PS) samples, experiments to verify this effect are conducted. The results show that under short pulses of 10 ns, all the samples fail due to bulk breakdown, whereas when the pulse width is tuned to a long pulse of 7 μs, the samples fail as a result of surface flashover. The experimental results are interpreted by analyzing the conditions for the bulk breakdown and the surface flashover. It is found that under short pulses, the flashover threshold would be as high as the bulk breakdown strength (EBD) and the flashover time delay (td) would be longer than the pulse width (τ), both of which make the dielectrics' cumulative breakdown occur easily; whereas under long pulses, that Ef is much lower than EBD and td is smaller than τ is advantageous to the occurrence of the surface flashover. In addition, a general principle on solid insulation design under short pulse condition is proposed based on the experimental results and the theoretical analysis.

  13. Theoretical investigation of conductivity sensitivities of SiC-based bio-chemical acoustic wave sensors (United States)

    Fan, Li; Chen, Zhe; Zhang, Shu-yi; Zhang, Hui


    The phase velocities, electromechanical coupling coefficients, conductivity sensitivities, insert losses, and minimum detectable masses of Rayleigh and Lamb waves sensors based on silicon carbide (SiC) substrates are theoretically studied. The results are compared with the performances of the sensors based on conventional silicon substrates. It is found that the sensors using SiC substrates have higher electromechanical coupling coefficients and conductivity sensitivities than the conventional silicon-based sensors in virtue of piezoelectricity of the SiC. Moreover, higher phase velocities in SiC substrates can reduce the insert losses and minimum detectable masses of the sensors. In this case, in the detection of the gas with the tiny mass as the hydrogen, in which the conductivity sensitivity is more important than the mass sensitivity, the sensor based on the SiC substrate has a higher sensitivity and exhibits the potential to detect the gas with the concentration below the ppm level. According to the results, the performances of the sensors based on the Rayleigh and Lamb waves using the SiC substrates can be optimized by properly selecting piezoelectric films, structural parameters, and operating wavelengths.

  14. Theoretical and Experimental Investigations of the Potential of Osmotic Energy for Power Production † (United States)

    Sharif, Adel O.; Merdaw, Ali A.; Aryafar, Maryam; Nicoll, Peter


    This paper presents a study on the potential of osmotic energy for power production. The study includes both pilot plant testing and theoretical modelling as well as cost estimation. A projected cost of £30/MWh of clean electricity could be achieved by using a Hydro-Osmotic Power (HOP) plant if a suitable membrane is used and the osmotic potential difference between the two solutions is greater than 25 bar; a condition that can be readily found in many sites around the world. Results have shown that the membrane system accounts for 50%–80% of the HOP plant cost depending on the salinity difference level. Thus, further development in membrane technology and identifying suitable membranes would have a significant impact on the feasibility of the process and the route to market. As the membrane permeability determines the HOP process feasibility, this paper also describes the effect of the interaction between the fluid and the membrane on the system permeability. It has been shown that both the fluid physical properties as well as the membrane micro-structural parameters need to be considered if further development of the HOP process is to be achieved. PMID:25110959

  15. Theoretical and Experimental Investigations of the Potential of Osmotic Energy for Power Production

    Directory of Open Access Journals (Sweden)

    Adel O. Sharif


    Full Text Available This paper presents a study on the potential of osmotic energy for power production. The study includes both pilot plant testing and theoretical modelling as well as cost estimation. A projected cost of £30/MWh of clean electricity could be achieved by using a Hydro-Osmotic Power (HOP plant if a suitable membrane is used and the osmotic potential difference between the two solutions is greater than 25 bar; a condition that can be readily found in many sites around the world. Results have shown that the membrane system accounts for 50%–80% of the HOP plant cost depending on the salinity difference level. Thus, further development in membrane technology and identifying suitable membranes would have a significant impact on the feasibility of the process and the route to market. As the membrane permeability determines the HOP process feasibility, this paper also describes the effect of the interaction between the fluid and the membrane on the system permeability. It has been shown that both the fluid physical properties as well as the membrane micro-structural parameters need to be considered if further development of the HOP process is to be achieved.

  16. Emotion felt by the listener and expressed by the music: a literature review and theoretical investigation

    Directory of Open Access Journals (Sweden)

    Emery eSchubert


    Full Text Available In his seminal paper, Gabrielsson (2002 distinguishes between emotion felt by the listener, here: ‘internal locus of emotion’ (IL, and the emotion the music is expressing, here: 'external locus emotion' (EL. This paper tabulates 16 such publications published in the decade 2003-2012 consisting of 19 studies/experiments and provides some theoretical perspectives. The key findings were that (1 IL ratings was frequently rated statistically the same or lower than the corresponding EL rating (e.g. lower felt happiness rating compared to the apparent happiness of the music, and that (2 self-select and preferred music had a smaller gap across the emotion loci than experimenter selected and disliked music. These key findings were explained by an ‘inhibited’ emotional contagion mechanism, where the otherwise matching felt emotion may have been attenuated by some other factor such as social context. Matching between EL and IL for loved and self-selected pieces was explained by the activation of ‘contagion’ circuits. Physiological arousal, personality and age, as well as musical features (tempo, mode, putative emotions were observed to influence perceived and felt emotion distinctions. A variety of data collection formats were identified, but mostly using continuous rating scales. In conclusion, a more systematic use of terminology appears desirable with respect to theory-building. Whether two broad categories, namely matched and unmatched, are sufficient to capture the relationships between EL and IL, instead of four categories as suggested by Gabrielsson, is subject to future research.

  17. Spectral investigation and theoretical study of zwitterionic and neutral forms of quinolinic acid (United States)

    Karabacak, M.; Sinha, L.; Prasad, O.; Bilgili, S.; Sachan, Alok K.; Asiri, A. M.; Atac, A.


    In this study, molecular structure and vibrational analysis of quinolinic acid (2,3-pyridinedicarboxylic acid), in zwitterionic and neutral forms, were presented using FT-IR, FT-Raman, NMR, UV experimental techniques and quantum chemical calculations. FT-IR and FT-Raman spectra of 2,3-pyridinedicarboxylic acid (2,3-PDCA) in the solid phase were recorded in the region 4000-400 cm-1 and 3500-0 cm-1, respectively. The geometrical parameters and energies were obtained for zwitter and neutral forms by using density functional theory (DFT) at B3LYP/6-311++G(d,p) level of theory. 3D potential energy scan was performed by varying the selected dihedral angles using M06-2X and B3LYP functionals at 6-31G(d) level of theory and thus the most stable conformer of the title compound was determined. The most stable conformer was further optimized at higher level and vibrational wavenumbers were calculated. Theoretical vibrational assignment of 2,3-PDCA, using percentage potential energy distribution (PED) was done with MOLVIB program. 13C and 1H NMR spectra were recorded in DMSO. Chemical shifts were calculated at the same level of theory. The UV absorption spectra of the studied compound in ethanol and water were recorded in the range of 200-400 nm. The optimized geometric parameters were compared with experimental data.

  18. An Experimental and Theoretical Investigation of Ultrasound Transmission in Bubbly PDMS Phononic Crystals (United States)

    Christianson, Caleb; Mukhopadhyay, Saikat; Sachse, Wolfgang; Stewart, Derek


    Phononic crystals are two- and three-dimensional structures with a periodic arrangement of two or more materials with different acoustic properties. Depending on the size, structure, and characteristics of the constituent materials, metamaterials with interesting acoustic properties can be formed. These crystals can be used to control the transmission of sound at selected frequencies, focus sound, or serve as waveguides. In this talk, we will focus on the transmission of ultrasonic waves through polydimethylsiloxane (PDMS) films with entrapped air bubbles. Two different theoretical models were used to predict ultrasonic transmission through air-PDMS crystals: (1) a simple scattering model for a series of partially reflective thin films and (2) the code MULTEL, which calculates the transmission using multiple scattering theory. A fabrication process was also developed to stack layers of the crystals with unprecedented alignment. We measured the ultrasonic transmission through the films using the ultrasonic through-transmission mode in a water bath and found an excellent agreement between the measured and calculated transmission. Additionally, we used these models to predict the performance of new phononic structures by scanning a large parameter space and showed how ultrasonic transmission through PDMS layers can be engineered by varying the dimensions, separation, and arrangement of air bubbles. This work was supported by the National Science Foundation.

  19. Theoretical investigation of alignment-dependent intense-field fragmentation of acetylene (United States)

    Doblhoff-Dier, Katharina; Kitzler, Markus; Gräfe, Stefanie


    We analyze the alignment-dependent dissociative and nondissociative ionization of acetylene, C2H2 . Numerical models describing the yield of the singly and doubly charged ions (C2H2+,C2H22 +) and several fragmentation and isomerization channels (C2H++H+ ,CH++CH+ ,CH2++C+ ) as a function of the relative alignment angle between the laser polarization axis and the molecular axis are presented. We apply and compare two different approaches. The first is based on time-dependent density functional theory. The second is a quasi-single-particle approach using the Dyson orbitals. We find good agreement between the results of both methods. A comparison of our theoretical predictions with experimental data allows us to show that the alignment-dependent yield of most reaction channels is described to high accuracy assuming sequential ionization. However, for some of the fragmentation channels, namely, CH++CH+ and C2H++H+ , we find non-negligible influence of recollisional ionization.

  20. An experimental and theoretical investigation of particle–wall impacts in a T-junction

    KAUST Repository

    Vigolo, D.


    Understanding the behaviour of particles entrained in a fluid flow upon changes in flow direction is crucial in problems where particle inertia is important, such as the erosion process in pipe bends. We present results on the impact of particles in a T-shaped channel in the laminar-turbulent transitional regime. The impacting event for a given system is described in terms of the Reynolds number and the particle Stokes number. Experimental results for the impact are compared with the trajectories predicted by theoretical particle-tracing models for a range of configurations to determine the role of the viscous boundary layer in retarding the particles and reducing the rate of collision with the substrate. In particular, a two-dimensional model based on a stagnation-point flow is used together with three-dimensional numerical simulations. We show how the simple two-dimensional model provides a tractable way of understanding the general collision behaviour, while more advanced three-dimensional simulations can be helpful in understanding the details of the flow. © 2013 Cambridge University Press.

  1. Theoretical and Experimental Investigation of Quantum Confinement Effect on the Blue Shift in Semiconductor Quantum Dots

    Directory of Open Access Journals (Sweden)

    Changiz. Vatankhah


    Full Text Available Nano particles of zinc sulfide (ZnS of face centered cubic (fcc structures were synthesized using sulphur source of soium sulphide and mercaptoethanol respectively via Chemical Bath Deposition method. The synthesized quantum dots were characterized using X-ray diffraction (XRD, transmission electron microscopy (TEM and UV-visible spectrophotometry. The average crystallite size calculated from TEM and XRD pattern has been found to in the range 4.6 – 1.9 nm, the pariticles size decreases with the increase of the capping agent concentrations from 0. 001 to 0.7 Mol. The absorption coefficient in the range 325 - 250 nm decreases with increasing capping agent and the particles. ZnS nanoparticles were also derived from time independent Schrodinger equations for ZnS system and calculated the coefficient absorption using the density functional theory (DFT . It is shown that decreasing of ZnS nanosize lead to changes the optical properties and coefficient absorption in the visible region does not occur and the particles act like a transparent material. In this work, the blue shift was observed in absorption-wavelength both theoretical and experimental method due to the quantum confinement effects.

  2. Surface plasmon engineering in graphene functionalized with organic molecules: a multiscale theoretical investigation. (United States)

    Cheng, Jierong; Wang, Wei Li; Mosallaei, Hossein; Kaxiras, Efthimios


    Graphene was recently shown to support deep subwavelength surface plasmons at terahertz frequencies characterized by low energy loss and strong field localization, both highly desirable. The properties of graphene can be locally tuned by applying an external gate voltage or by the adsorption of organic molecules that lead to doping through charge transfer. Local tuning of the electronic features of graphene opens the possibility to realize any desired gradient index profile and thus brings large flexibility to control and manipulate the propagation of surface plasmons. Here, we explore this possibility created by functionalizing graphene with organic molecules. We employ a multiscale theoretical approach that combines first-principles electronic structure calculations and finite-difference time-domain simulations coupled by surface conductivity. We show that by patterning two types of organic molecules on graphene, a plasmonic metasurface can be realized with any gradient effective refractive index profile to manipulate surface plasmon beams as desired. The special properties of such devices based on functionalized graphene are compared to the similar metamaterials based on metallic films on top of a gradient index dielectric substrate. Using this idea, we design and analyze an ultrathin broadband THz plasmonic lens as proof-of-concept, while more sophisticated index profiles can also be realized and various plasmonic applications are readily accessible.

  3. Theoretical and experimental investigation on magneto-hydrodynamics of plasma window

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S. Z.; Zhu, K., E-mail:; Huang, S.; Lu, Y. R.; Yuan, Z. X.; Shi, B. L.; Gan, P. P. [State Key Laboratory of Nuclear Physics and Technology, Peking University, Beijing 100871 (China); Hershcovitch, A. [Brookhaven National Laboratory, Upton, New York 11973-5000 (United States)


    As a new device, plasma window has been designed to use plasma discharge to separate atmosphere from vacuum with high difference of pressure. It has many excellent properties, being able to be used as available passage for ion beam with negligible energy loss, also impervious to radiation damage and thermal damage. Normally beam focusing by accelerators is not that easy to achieve within channel of small cross section. 10 mm diameter plasma window's experimental realization could contribute to its further application in accelerator system. In this paper, 10 mm diameter 60 mm long plasma window has first been designed and managed to generate arc discharge with argon gas experimentally. The result proves that it has the ability to separate at least 28.8 kPa (not the upper limit) from 360 Pa with 50 A direct current and 2.5 kW power supplied. Current increase leads to linear inlet pressure increase obviously, while it has less impact on outlet pressure and voltage, coming to the conclusion that the higher current of plasma discharge, the larger pressure difference it creates. Theoretical analysis of 10 mm diameter plasma window in axis symmetrical configuration using argon also has been provided, in which a numerical 2D FLUENT-based magneto-hydrodynamic simulation model is settled. It has a good agreement with experimental result on voltage and mass flow rate when inlet pressure is increased.

  4. [Investigations in dynamics of gauge theories in theoretical particle physics]. [Virginia Polytechnic Institute State Univ. , Blacksburg

    Energy Technology Data Exchange (ETDEWEB)


    The major theme of the theoretical physics research conducted under DOE support over the past several years has been within the rubric of the standard model, and concerned the interplay between symmetries and dynamics. The research was thus carried out mostly in the context of gauge field theories, and usually in the presence of chiral fermions. Dynamical symmetry breaking was examined both from the point of view of perturbation theory, as well as from non-perturbative techniques associated with certain characteristic features of specific theories. Among the topics of research were: the implications of abelian and non-abelian anomalies on the spectrum and possible dynamical symmetry breaking in any theory, topological and conformal properties of quantum fields in two and higher dimensions, the breaking of global chiral symmetries by vector-like gauge theories such as QCD, the phenomenological implications of a strongly interacting Higgs sector in the standard model, and the application of soliton ideas to the physics to be explored at the SSC.

  5. Enhancement in dehydriding performance of magnesium hydride by iron incorporation: A combined experimental and theoretical investigation (United States)

    Chen, Haipeng; Yu, Hao; Zhang, Qianqian; Liu, Bogu; Liu, Pei; Zhou, Xinpei; Han, Zongying; Zhou, Shixue


    Structural change and dehydriding mechanism of MgH2 with atomic Fe incorporation from reactive ball milling are characterized and simulated by first-principles calculation. Two kinds of hydrides β- and γ-MgH2 are formed from Mg powders under hydrogen atmosphere by 3.0 h of milling with pretreated anthracite as milling aid. Experimental studies suggest that the atomic Fe can be incorporated onto MgH2 surface by the shearing effect of Fe-based milling balls on Mg/MgH2 particles. The incorporated Fe has a high dispersity on MgH2 surface and can form atomic clusters FeH4/FeH2 by combining with H anions. The dehydriding reaction of the Fe-incorporated MgH2 begins at hydride surface and shows an enhanced performance with apparent activation energy of 110.3 kJ mol-1. Theoretical studies suggest that the incorporated Fe can act as a bridge that contributes to electron transfer from H anion to Mg cation before H2 molecule formation. The intrinsic reason of atomic Fe in catalyzing dehydriding reaction of MgH2 lies in its moderate strength of electron attraction.

  6. Chromatography methods in investigation of lipophilicity of the biological active substances


    Odović Jadranka V.; Trbojević-Stanković Jasna B.


    This paper presents the review of the methods used in research of the biological active substances hydrophobicity, a very important property. The biological activity of some substances depends on their pharmacokinetics and pharmacodynamics. These processes depend on the molecule's capability to interact with two different media: aqueous (cells interior) and non-aqueous (cells membrane), or on the molecule lipophilicity. Today, great attention is given to investigation and systematic determina...

  7. Experimental and theoretical investigation on the interaction between cyclovirobuxine D and human serum albumin (United States)

    Yue, Yuanyuan; Liu, Ren; Liu, Jianming; Dong, Qiao; Fan, Jing


    Cyclovirobuxine D is an active compound extracted from the plant Buxux microphylla, and widely available as medications; however, its abuse may casts potential detrimental effects on human health. By using multispectroscopic techniques and molecular modeling, the interaction of cyclovirobuxine D with human serum albumin was investigated. The fluorescence results manifested that static type was the operative mechanism for the interaction with human serum albumin. The structural investigation of the complexed HSA through CD, three-dimensional, FT-IR and synchronous fluorescence shown the polypeptide chain of HSA partially destabilizing. Docking studies revealed the molecule to be bound in the subdomain IIA. Finally, we investigated the distance between the bound ligand and Trp-214 of human serum albumin.

  8. Two-photon absorption of [2.2]paracyclophane derivatives in solution: A theoretical investigation (United States)

    Ferrighi, Lara; Frediani, Luca; Fossgaard, Eirik; Ruud, Kenneth


    The two-photon absorption of a class of [2.2]paracyclophane derivatives has been studied using quadratic response and density functional theories. For the molecules investigated, several effects influencing the two-photon absorption spectra have been investigated, such as side-chain elongation, hydrogen bonding, the use of ionic species, and solvent effects, the latter described by the polarizable continuum model. The calculations have been carried out using a recent parallel implementation of the polarizable continuum model in the DALTON code. Special attention is given to those aspects that could explain the large solvent effect on the two-photon absorption cross sections observed experimentally for this class of compounds.

  9. Gas chromatography (United States)

    Guiochon, Georges; Guillemin, Claude L.


    Gas chromatography is a powerful separation technique for gas and vapor mixtures. Combining separation and on-line detection permits accurate quantitative analysis of complex mixtures, including traces of compounds down to parts per trillions in some particular cases. The importance of gas chromatography in quality control and process control in the chemical and drug industry, in environmental pollution investigations and in clinical analysis is critical. The principles of the technique are discussed, the main components of a gas chromatograph are described and some idea of the importance of the applications is given.

  10. X-ray diffraction and theoretical investigation of the Gedunin crystal structure (United States)

    Carvalho, Paulo S.; Napolitano, Hamilton B.; Camargo, Ademir J.; Silva, Valter H. C.; Ellena, Javier A.; Rocha, Waldireny C.; Vieira, Paulo C.


    The Gedunin compound (C 28H 34O 6) is a natural product extracted from Trichilia pallida that has shown a wide activity. The crystallographic structure shows two conformers in the asymmetric unit, which differ in a rotation of the furan group. To understand this molecular arrangement, the density functional calculations, Molecular Electrostatic Potential (MEP) and thermodynamic function calculation have been performed at the B3LYP/6-311++g(d,p) level. Both conformers were optimized and the agreement with the experimental structure was very good, making possible further theoretical analysis of the structure. The inter-conversion between two conformers depends on the energy barrier. This process is studied in the vacuum and shows two transition states with a low energetic barrier for a potential energy curve scanning rigid around furan group: 4.37 kcal/mol and 16.52 kcal/mol. As the first transition state has a notably lower energetic barrier, the preferred inter-conversion pathway between the conformers involves the first rather than the second transition state. Understanding this transition state in detail led us to perform its optimization, showing an energetic barrier around 3.66 kcal/mol. The negative free energy and low enthalpy confirm that the process is spontaneous and exothermic. The results show that this requirement makes the existence of the two conformers in the asymmetric unit possible. The structure of molecules in the asymmetric unit is better understood when the MEP is used on the interaction between molecules. For Gedunin, both molecules have shown MEP with well-defined regions, and this behavior contributes to the observed link between molecules and for the negative regions complementing positive regions of another molecule.

  11. DFT theoretical investigations of π-conjugated molecules based on thienopyrazine and different acceptor moieties for organic photovoltaic cells

    Directory of Open Access Journals (Sweden)

    Mohammed Bourass


    Full Text Available In this work, theoretical study by using the DFT method on eleven conjugated compounds based on thienopyrazine is reported. Different electron side groups were introduced to investigate their effects on the electronic structure; The HOMO, LUMO and Gap energy of these compounds have been calculated and reported in this paper. A systematic theoretical study of such compound has not been reported as we know. Thus, our aim is first, to explore their electronic and spectroscopic properties on the basis of the DFT quantum chemical calculations. Second, we are interested to elucidate the parameters that influence the photovoltaic efficiency toward better understanding of the structure–property relationships. The study of structural, electronic and optical properties for these compounds could help to design more efficient functional photovoltaic organic materials.

  12. Organizational culture and organizational effectiveness: a meta-analytic investigation of the competing values framework's theoretical suppositions. (United States)

    Hartnell, Chad A; Ou, Amy Yi; Kinicki, Angelo


    We apply Quinn and Rohrbaugh's (1983) competing values framework (CVF) as an organizing taxonomy to meta-analytically test hypotheses about the relationship between 3 culture types and 3 major indices of organizational effectiveness (employee attitudes, operational performance [i.e., innovation and product and service quality], and financial performance). The paper also tests theoretical suppositions undergirding the CVF by investigating the framework's nomological validity and proposed internal structure (i.e., interrelationships among culture types). Results based on data from 84 empirical studies with 94 independent samples indicate that clan, adhocracy, and market cultures are differentially and positively associated with the effectiveness criteria, though not always as hypothesized. The findings provide mixed support for the CVF's nomological validity and fail to support aspects of the CVF's proposed internal structure. We propose an alternative theoretical approach to the CVF and delineate directions for future research.

  13. A Theoretical Investigation of the Effect of Pressure on the Structural, Elastic and Mechanical Properties of ZnS Crystals (United States)

    Güler, E.; Güler, M.


    Structural, elastic, and mechanical properties of blende-type zinc sulfide ( bt-ZnS) were investigated under pressures up to 20 GPa. Unlike previous theoretical calculations, an existing mixed-type interatomic potential was applied with geometry optimization calculations. B3 → B1 phase transition pressure was obtained as 17 GPa under zero pressure and temperature. Pressure dependence of typical cubic elastic constants, bulk, shear and Young moduli, elastic wave velocities, Kleinman parameter, static and high-frequency dielectric constants of bt-ZnS were also obtained. Overall, our results for the considered parameters of bt-ZnS are in good agreement with experiments and better than those of several available theoretical data.

  14. Molecular and Cellular Quantitative Microscopy: theoretical investigations, technological developments and applications to neurobiology

    NARCIS (Netherlands)

    Esposito, Alessandro


    This PhD project aims at the development and evaluation of microscopy techniques for the quantitative detection of molecular interactions and cellular features. The primarily investigated techniques are Fαrster Resonance Energy Transfer imaging and Fluorescence Lifetime Imaging Microscopy. These tec

  15. Investigation of the theoretical load alleviation potential using trailing edge flaps controlled by inflow data

    DEFF Research Database (Denmark)

    Fischer, Andreas; Aagaard Madsen, Helge


    A novel control concept for fatigue load reduction with trailing edge flaps based on the measurement of the inflow locally on the blade was presented. The investigation was conducted with the aeroelastic code HAWC2. The aerodynamic modelling in the code is based on blade element momentum theory...

  16. Theoretical-methodological aspects of systemic geographical investigation into landscape degradation

    Directory of Open Access Journals (Sweden)

    Dušan Plut


    Full Text Available The following methodological approaches have been developed in the systemically planned investigation into the degradation of geographical environment: the physico-geographical, the ecosystemic, the socio-ecological, the landscape-ecological, and the functional regional-geographical ones.

  17. Theoretical investigation of reactions between ammonia and precursors from the ozonolysis of ethane

    DEFF Research Database (Denmark)

    Jørgensen, Solvejg; Gross, Allan


      The reaction mechanisms between ammonia and two secondary organic aerosol (SOA) precursors from ozonolysis of alkenes - namely the secondary ozonide (SOZ) and hydroxyl substituted ester (HSE) have been investigated using quantum mechanics calculations. For the reaction between ammonia and SOZ, ...

  18. Theoretical investigations of CO₂ and CH₄ sorption in an interpenetrated diamondoid metal-organic material.

    KAUST Repository

    Pham, Tony


    Grand canonical Monte Carlo (GCMC) simulations of CO2 and CH4 sorption and separation were performed in dia-7i-1-Co, a metal-organic material (MOM) consisting of a 7-fold interpenetrated net of Co(2+) ions coordinated to 4-(2-(4-pyridyl)ethenyl)benzoate linkers. This MOM shows high affinity toward CH4 at low loading due to the presence of narrow, close fitting, one-dimensional hydrophobic channels-this makes the MOM relevant for applications in low-pressure methane storage. The calculated CO2 and CH4 sorption isotherms and isosteric heat of adsorption, Qst, values in dia-7i-1-Co are in good agreement with the corresponding experimental results for all state points considered. The experimental initial Qst value for CH4 in dia-7i-1-Co is currently the highest of reported MOM materials, and this was further validated by the simulations performed herein. The simulations predict relatively constant Qst values for CO2 and CH4 sorption across all loadings in dia-7i-1-Co, consistent with the one type of binding site identified for the respective sorbate molecules in this MOM. Examination of the three-dimensional histogram showing the sites of CO2 and CH4 sorption in dia-7i-1-Co confirmed this finding. Inspection of the modeled structure revealed that the sorbate molecules form a strong interaction with the organic linkers within the constricted hydrophobic channels. Ideal adsorbed solution theory (IAST) calculations and GCMC binary mixture simulations predict that the selectivity of CO2 over CH4 in dia-7i-1-Co is quite low, which is a direct consequence of the MOM\\'s high affinity toward both CO2 and CH4 as well as the nonspecific mechanism shown here. This study provides theoretical insights into the effects of pore size on CO2 and CH4 sorption in porous MOMs and its effect upon selectivity, including postulating design strategies to distinguish between sorbates of similar size and hydrophobicity.


    Directory of Open Access Journals (Sweden)

    G. D. Liakhevich


    Full Text Available In Belarus concrete with strength up to 60 MPA is used for construction. At the same time high strength concrete with compressive strength above 60 MPA is widely used in all industrially developed countries. High- strength concrete is included in regulatory documents of the European Union and that fact has laid a solid foundation for its application. High strength concrete is produced using highly dispersed silica additives, such as micro-silica and plasticizers (super-plasticizers with a water/cement (w/c ratio not greater than 0.4.Theoretical aspects of high-strength concrete for bridge structures have been studied in the paper. The paper shows a positive impact of highly dispersed additives on structure and physico-mechanical properties of cement compositions, namely: reduction of total porosity of a cement stone in concrete while increasing volumetric concentration and dispersion of a filler; binding of calcium hydroxide with the help of amorphised micro-silica; increased activity of mineral additives during their thin shredding; acceleration of the initial stage of chemical hardening of cement compositions with highly dispersed particle additives that serve as centers of crystallization; “binder-additive” cluster formation due to high surface energy of highly dispersed additive particles; hardening of surface area between a cement stone and aggregates in concrete; high-strength concretes are gaining strength much faster than conventional concretes.Technology of preparation and composition of high-strength concrete using highly dispersed mineral additives and super-plasticizer has been developed in the paper. This concrete will ensure a higher density, wa- ter-and gas tightness, increased resistance to aggressive environment, reduced consumption of concrete and reinforcement, reduced transport and installation weight, increased initial strength, early easing of shutters and preliminary compression, increased length of bridge spans

  20. Theoretical and experimental investigations on fracture statistics carried out at the IDIEM (Chile

    Directory of Open Access Journals (Sweden)

    Kittl, P.


    Full Text Available The high exigencies required for some structures owing to their responsability or their high cost have originated a new discipline that can be called Reability Engineering, which main aim is to determine the probability afforded by a machine to comply a requirement. This work contains a not fully detailed description of the topics studied by IDEM during those last years, within this field. Within it there are Fracture Statistics, which studies the probability for some structure to undergo plastic deformations, and the probability of the causes to occur, taken into account materials fatigue. It also includes a theoretical development of the fracture statistics, describing the specific-risk-of-fracture functions by means of integral equations, and the determination of their parameters and their uncertainties, when the functions have a known analytical form. Experimental researches range from the most brittle bodies, such as glass, almost brittle ones such as cement paste and to others that can admit plastic deformation, such as certain weldings, enlarging the study to fibro-composites and natural materials such as granite.

    Las altas exigencias requeridas para algunas estructuras de especial responsabilidad o de muy alto coste han dado origen a una nueva disciplina que puede denominarse Ingeniería de la Fiabilidad, cuyo principal objetivo es determinar la probabilidad con que un ingenio puede verificar una exigencia. En este trabajo se presenta una descripción, no muy detallada, de los tópicos tratados por el IDIEM, en estos últimos años, dentro de esta disciplina. Dentro de ella está la Mecánica Estadística de Fractura, que estudia la probabilidad de que una estructura se deforme plásticamente, y la probabilidad de ocurrencia de las causas, teniendo en cuenta la fatiga de los materiales. Se incluye un desarrollo teórico de la mecánica estadística de fractura, describiendo las funciones de riesgo específico de

  1. An Empirical Investigation into the Matching Problems among Game Theoretically Coordinating Parties in a Virtual Organization

    Directory of Open Access Journals (Sweden)

    Muhammad Tanweer Abdullah


    Full Text Available

    Virtual organization emerged as a highly flexible structure in response to the rapidly changing environment of 20th century. This organization consists of independently working parties that combine their best possible resources to exploit the emerging market opportunities. There are no formal control and coordination mechanisms employed by the classical hierarchical structures. Parties, therefore, manage their dependencies on each other through mutual understanding and trust.

    Mathematician John Nash, having significant contributions in Game Theory suggests that in every non-cooperative game there is at least one equilibrium point. At this point, according to him, every strategy of the player represents a response to the others’ strategies. Such equilibria could exist in a virtual organization, at which parties coordinate which each other to optimize their performance.

    Coordination/Matching problems are likely to arise among game theoretically coordinating parties in a virtual organization, mainly due to lack of binding agreements. By identifying and resolving these matching problems, virtual organizations could achieve efficiency and better coordination among parties.  

  2. Azomethine diimides end-capped with anthracene moieties: Experimental and theoretical investigations (United States)

    Schab-Balcerzak, Ewa; Grucela, Marzena; Malecki, Grzegorz; Kotowicz, Sonia; Siwy, Mariola; Janeczek, Henryk; Golba, Sylwia; Praski, Aleksander


    New arylene bisimide derivatives containing imine linkages and anthracene units were synthesized. Azomethine diimides were prepared via condensation reaction of 9-anthracenecarboxaldehyde and diamines with phthalic diimide or naphthalene diimide core and Schiff base linkers. They were characterized by FTIR spectroscopy, elemental analysis and mass spectrometry (MALDI-TOF-MS). The synthesized compounds exhibited high resistance against thermal decomposition up to 400 °C. Investigated compounds are electrochemically active and undergo reversible electrochemical reduction and irreversible oxidation processes as was found in cyclic voltammetry studies. The photoluminescence measurements of synthesized compounds in solid state as thin film on glass substrate revealed their ability to emission of the blue light with quantum yield efficiency about 2%. The electronic structure and spectroscopic properties of prepared azomethine diimides were also calculated by the density functional theory (DFT). The electrical properties of the diimide derivatives were preliminary investigated by current-voltage measurements.

  3. Experimental and theoretical investigation of the complexation of methacrylic acid and diisopropyl urea (United States)

    Pogány, Peter; Razali, Mayamin; Szekely, Gyorgy


    The present paper explores the complexation ability of methacrylic acid which is one of the most abundant functional monomer for the preparation of molecularly imprinted polymers. Host-guest interactions and the mechanism of complex formation between methacrylic acid and potentially genotoxic 1,3-diisopropylurea were investigated in the pre-polymerization solution featuring both experimental (NMR, IR) and in silico density functional theory (DFT) tools. The continuous variation method revealed the presence of higher-order complexes and the appearance of self-association which were both taken into account during the determination of the association constants. The quantum chemical calculations - performed at B3LYP 6-311 ++G(d,p) level with basis set superposition error (BSSE) corrections - are in agreement with the experimental observations, reaffirming the association constants and justifying the validity of computational investigation of such systems. Furthermore, natural bond orbital analysis was carried out to appraise the binding properties of the complexes.

  4. Theoretical investigation of the atomic and electronic structure of amino acids on Si(100) surfaces (United States)

    Luo, Xuan; Qian, Gefei; Sagui, Celeste; Roland, Christopher


    There are currently considerable efforts underway to combine silicon-based device technology with myriad of organic molecules, thereby fabricating new structures that take advantage of the tunable electronic and optical properties of organic molecules. A key aspect of this integration process is binding of the organics to the silicon surfaces. As part of this effort, we have been investigating the binding of several amino acids -- the building blocks for proteins -- on the Si (100) surface with state-of-the art density functional theory methods. Specifically, the binding between the buckled Si(100) and the NH2, CH2, COOH, C=0 and NC entities at various surface sites have been investigated. We report and discuss on the resulting structures and their electronic properties.

  5. Molecular and Cellular Quantitative Microscopy: theoretical investigations, technological developments and applications to neurobiology (United States)

    Esposito, Alessandro


    This PhD project aims at the development and evaluation of microscopy techniques for the quantitative detection of molecular interactions and cellular features. The primarily investigated techniques are Fαrster Resonance Energy Transfer imaging and Fluorescence Lifetime Imaging Microscopy. These techniques have the capability to quantitatively probe the biochemical environment of fluorophores. An automated microscope capable of unsupervised operation has been developed that enables the investigation of molecular and cellular properties at high throughput levels and the analysis of cellular heterogeneity. State-of-the-art Förster Resonance Energy Transfer imaging, Fluorescence Lifetime Imaging Microscopy, Confocal Laser Scanning Microscopy and the newly developed tools have been combined with cellular and molecular biology techniques for the investigation of protein-protein interactions, oligomerization and post-translational modifications of α-Synuclein and Tau, two proteins involved in Parkinson’s and Alzheimer’s disease, respectively. The high inter-disciplinarity of this project required the merging of the expertise of both the Molecular Biophysics Group at the Debye Institute - Utrecht University and the Cell Biophysics Group at the European Neuroscience Institute - Gαttingen University. This project was conducted also with the support and the collaboration of the Center for the Molecular Physiology of the Brain (Göttingen), particularly with the groups associated with the Molecular Quantitative Microscopy and Parkinson’s Disease and Aggregopathies areas. This work demonstrates that molecular and cellular quantitative microscopy can be used in combination with high-throughput screening as a powerful tool for the investigation of the molecular mechanisms of complex biological phenomena like those occurring in neurodegenerative diseases.

  6. Band theoretical investigation of substituted CrO2 within the local density approximation



    The effects of substitutions at différent concentrations within the lattice of CrO2 are investigated assuming ordered configurations. For this purpose we use self-consistent band structure calculations based on the local spin density approximation. All results show an antiparallel spin alignment between host Cr and the substitutional M = Ir, Os, Pt. Depending on the nature of M and its concentration, CrO2 transforms from a half metallic ferromagnet to a halfmetallic or metallic ferrimagnet.


    Institute of Scientific and Technical Information of China (English)


    A dynamic analysis approach to investigate the state of load distribution among contact bearings of double circular arc helical gears is proposed and a computer program is developed for calculating the factor of load distribution based on the theory of WN gears. The changing situations of load distribution among contact bearings of the gears influenced by main issues are analyzed by a series of parametric studies.

  8. Theoretical Investigation of Substituent Effects on the Dihydroazulene/Vinylheptafulvene Photoswitch: Increasing the Energy Storage Capacity. (United States)

    Hansen, Mia Harring; Elm, Jonas; Olsen, Stine T; Gejl, Aske Nørskov; Storm, Freja E; Frandsen, Benjamin N; Skov, Anders B; Nielsen, Mogens Brøndsted; Kjaergaard, Henrik G; Mikkelsen, Kurt V


    We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent dihydroazulene and vinylheptafulvene compounds. We wish to increase the energy storage capacity, that is, the energy difference between the dihydroazulene and vinylheptafulvene isomers, of the photoswitch by computational molecular design and have performed over 9000 electronic structure calculations using density functional theory. Based on these calculations, we obtain design rules for how to increase the energy storage capacity of the photoswitch. Furthermore, we have investigated how the activation energy for the thermally induced vinylheptafulvene to dihydroazulene conversion depends on the substitution pattern, and based on these results, we have outlined molecular design considerations for obtaining new desired target structures exhibiting long energy storage times. Selected candidate systems have also been investigated in terms of optical properties to elucidate how sensitive the absorption maxima are to the functionalizations.

  9. Theoretical Investigations of the Effects of Lithium Intercalation on the Properties of Indium Selenide (United States)

    Gomes da Costa, Manuel Pedro Fernandes

    The effect of intercalating lithium into gamma-InSe and beta -InSe has been investigated. The energy bands of pure gamma -InSe and pure beta-InSe were calculated using an overlap-reduced semi-empirical tight-binding method. The parameters for the interactions of Li atoms with In and Se atoms were obtained using the atomic wave-functions of Clementi and Roetti and the Heine-Abarenkov model potential. We established the positions of minimum potential inside the unit cell of the two InSe polytypes where the lithium atoms are most likely to be found. By placing lithium atoms in these sites, we calculated the modifications of the energy bands produced by the introduction of one Li atom per unit cell in gamma-InSe and two lithium atoms per unit cell in beta -InSe. The activation energy for movement of a Li atom between local energy minima was also calculated. The results have been correlated with the optical absorption and photoluminescence data of InSe and Li-intercalated InSe. The lattice dynamics of both the pure gamma- and beta-polytypes of the layer compound InSe have been investigated using a model containing short-range central forces and long -range Coulomb interactions. The normal mode frequencies and eigenvectors were determined by diagonalizing the dynamical matrix. The results have been correlated with the infrared and Raman spectra in InSe. The procedure was then extended to include one lithium ion per unit cell in a site of minimum potential in both the gamma-InSe and the beta-InSe polytypes. The effect of intercalated Li atoms on the vibrational modes and on the infrared and Raman spectra was then investigated.

  10. Field emission properties of capped carbon nanotubes doped by alkali metals:a theoretical investigation

    Institute of Scientific and Technical Information of China (English)

    Jin Lei; Fu Hong-Gang; Xie Ying; Yu Hai-Tao


    The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.

  11. Theoretical investigations on the elastic and thermodynamic properties of rhenium phosphide

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Qun; Zhu, Xuanmin; Lin, Zhengzhe; Yao, Ronghui [Xidian Univ., Xi' an (China). School of Physics and Optoelectronic Engineering; Yan, Haiyan [Baoji Univ. of Arts and Sciences (China). Dept. of Chemistry and Chemical Engineering


    Structural, mechanical, and electronic properties of orthorhombic rhenium phosphide (Re{sub 2}P) are systematically investigated by using first principles calculations. The elastic constants and anisotropy of elastic properties are obtained. The metallic character of Re{sub 2}P is demonstrated by density of state calculations. The quasi-harmonic Debye model is applied to the study of the thermodynamic properties. The thermal expansion, heat capacities, and Grueneisen parameter on the temperature and pressure have been determined as a function of temperature and pressure in the pressure range from 0 to 100 GPa and the temperature range from 0 to 1600 K.

  12. Theoretical investigation on the magnetocaloric effect in amorphous Eu80 Au20 system (United States)

    Costa, S. S.; Roriz, O. A. V.; Silvano, N. de O.; von Ranke, P. J.; Nóbrega, E. P.


    In this work, we investigated the magnetic and magnetocaloric properties of the amorphous system Eu80 Au20. The magnetic state equation and entropy were considered in the framework of Handrich-Kaneyoshi model, which takes into account the amorphization through the symmetric exchange fluctuation in the mean field approximation. The exchange and structural fluctuations parameters were chosen based on the experimental data of Eu80 Au20. The isothermal entropy change was calculated for several variations of external magnetic field. Furthermore, the adiabatic temperature change and the refrigerant capacity were calculated for a magnetic field change from 0 to 5 T.

  13. Theoretical investigation of the thermoelectric transport properties of BaSi2

    Institute of Scientific and Technical Information of China (English)

    Peng Hua; Wang Chun-Lei; Li Ji-Chao; Zhang Rui-Zhi; Wang Hong-Chao; Sun Yi


    The full-potential linear augmented plane wave method based on density functional theory is employed to investigate the electronic structure of BaSi2 With the constant relaxation time and rigid band approximation, the electrical conductivity, Seebeck coefficient and figure of merit are calculated by using Boltzmann transport theory, further evaluated as a function of carrier concentration. We find that the Seebeck coefficient is more anisotropic than electrical conductivity. The figure of merit of BaSi2 is predicted to be quite high at room temperature, implying that optimal doping may be an effective way to improve thermoelectric properties.

  14. New materials based on carbazole for optoelectronic device applications:Theoretical investigation

    Institute of Scientific and Technical Information of China (English)

    K.Hasnaoui; H.Zgou; M.Hamidi; M.Bouachrine


    A quantum-chemical investigation on the structural and optoelectronic properties of two materials based on carbazole is carried out.The purpose is to display the effect of grafting the fluorine atoms on their optoelectronic and pbysico-chemical properties.In addition to solubility in the polar solvents and the modification in geometric parameters,the substitution of fluorine destabilizes the HOMO and LUMO levels,decreases the band gap energy and raises conjugation length.These properties suggest the substituted fluorine compound as a good candidate for optoelectronic applications.


    DEFF Research Database (Denmark)

    Jordan, Ulrike; Shah, Louise Jivan; Furbo, Simon


    Advanced experimental methods were applied to study flow structures of a water jet entering a tank from the bottom. A squared experimental glass tank with a volume of about 140 l was used. Above the inlet pipe a flat plate was installed, as shown in the figure. The goal of the investigations...... is to study the influence of the inlet device geometry and of the operating conditions (the flow rate, draw-off volume, and temperatures) on the thermal stratification in the tank. Measurements of the flow and temperature fields were carried out with two visualization techniques: - To visualize the flow field...

  16. a Theoretical Investigation on 10-12 Potential of Hydrogen-Hydrogen Covalent Bond (United States)

    Taneri, Sencer


    This is an analytical investigation of well-known 10-12 potential of hydrogen-hydrogen covalent bond. In this research, we will make an elaboration of the well-known 6-12 Lennard-Jones potential in case of this type of bond. Though the results are illustrated in many text books and literature, an analytical analysis for these potentials is missing almost everywhere. The power laws are valid for small radial distances, which are calculated to some extent. The internuclear separation as well as the binding energy of the hydrogen molecule are evaluated with success.

  17. Theoretical investigation of boundary contours of ground-state atoms in uniform electric fields (United States)

    Shi, Hua; Zhao, Dong-Xia; Yang, Zhong-Zhi


    The boundary contours were investigated for first 54 ground-state atoms of the periodic table when they are in uniform electric fields of strengths 106, 107 and 108 V/m. The atomic characteristic boundary model in combination with an ab-initio method was employed. Some regularities of the deformation of atoms, ΔR, in above electric fields are revealed. Furthermore, atomic polarisabilities of the first 54 elements of the periodic table are shown to correlate strongly with the mean variation rate of atomic radial size divided by the strength of the electric field F, ?, which provides a predictive method of calculating atomic polarisabilities of 54 atoms.

  18. Investigation of protein selectivity in multimodal chromatography using in silico designed Fab fragment variants. (United States)

    Karkov, Hanne Sophie; Krogh, Berit Olsen; Woo, James; Parimal, Siddharth; Ahmadian, Haleh; Cramer, Steven M


    In this study, a unique set of antibody Fab fragments was designed in silico and produced to examine the relationship between protein surface properties and selectivity in multimodal chromatographic systems. We hypothesized that multimodal ligands containing both hydrophobic and charged moieties would interact strongly with protein surface regions where charged groups and hydrophobic patches were in close spatial proximity. Protein surface property characterization tools were employed to identify the potential multimodal ligand binding regions on the Fab fragment of a humanized antibody and to evaluate the impact of mutations on surface charge and hydrophobicity. Twenty Fab variants were generated by site-directed mutagenesis, recombinant expression, and affinity purification. Column gradient experiments were carried out with the Fab variants in multimodal, cation-exchange, and hydrophobic interaction chromatographic systems. The results clearly indicated that selectivity in the multimodal system was different from the other chromatographic modes examined. Column retention data for the reduced charge Fab variants identified a binding site comprising light chain CDR1 as the main electrostatic interaction site for the multimodal and cation-exchange ligands. Furthermore, the multimodal ligand binding was enhanced by additional hydrophobic contributions as evident from the results obtained with hydrophobic Fab variants. The use of in silico protein surface property analyses combined with molecular biology techniques, protein expression, and chromatographic evaluations represents a previously undescribed and powerful approach for investigating multimodal selectivity with complex biomolecules.

  19. Theoretical investigation of superconductivity in MgB2-xCx alloys (United States)

    Sharma, Gargee; Sharma, Smita


    In this paper we investigated the superconducting properties of MgB2-xCx alloys where x is the concentration (0.0, 0.03, 0.11 and 0.20). The superconducting state parameters, namely, the electron-phonon coupling strength (λ), Coulomb pseudopotential (μ*), transition temperature (Tc), isotope effect exponent (α) and interaction strength (NoV) of MgB2-xCx alloys have been investigated in the BCS-Eliashberg-McMillan framework, as modified for MgB2-xCx alloys. Pseudo ions with average properties have been considered to replace different types of ions in the system. It is observed that all the superconducting parameters go on decreasing as the concentration of C is increased. The magnitudes of λ and Tc indicate that MgB2-xCx is strong-to-intermediate coupling superconductor. It is also observed that Tc is composition dependent. Present computations yield almost linear variation of Tc with concentration x of C in the MgB2-xCx system, which is in agreement with the experimental data. A linear Tc equation is proposed by fitting the present results.

  20. Interactions of small gold clusters, Aun (n=1-3), with graphyne: theoretical investigation. (United States)

    Azizi, Elmira; Tehrani, Zahra Aliakbar; Jamshidi, Zahra


    The interactions of gold atom and clusters (Au2 and Au3) with the active sites of graphyne (GY) have been investigated using density functional theory (PBE, PBE-D3, and B3LYP-D3). In order to compare performance of DFT functional (BP86, PBE, TPSSh, B3LYP, PBE-D3, TPSSh-D3, and B3LYP-D3), the interactions of Au2 with various functional groups such as -sp, -sp(2) and aromatic sp(2) carbon atoms, -sp, -sp(2) and aromatic sp(2)-bonds have been investigated and also compared with the ab initio MP2 results. Additionally, the nature of interactions for graphyne-Au2 complexes are interpreted by means of the natural bond orbital (NBO), the quantum theory of atoms in molecules (QTAIM) and energy decomposition analysis (EDA) and compared with those of related graphene-Au2. This study suggests that graphyne shows complex behavior in comparison to those of graphene and could also be useful in modeling of the next generation electronic devices.

  1. Nonlinear optical switching behavior in the solid state: A theoretical investigation on anils

    KAUST Repository

    Ségerie, Audrey


    The linear (π(1)) and second-order nonlinear (π(2)) optical properties of two anil crystals, [N-(4-hydroxy)-salicylidene-amino-4-(methylbenzoate) and N-(3,5-di-tert- butylsalicylidene)-4-aminopyridine, denoted 4A and 4P, respectively], as well as the optical contrasts upon switching between their enol (E) and keto (K) forms, have been investigated by combining the molecular responses calculated using quantum chemistry methods and an electrostatic interaction scheme to account for the local field effects. It is found that intermolecular interactions impact differently the K/E optical contrasts in the two systems, which illustrates the importance of the supramolecular organization on the macroscopic responses. In 4A, the surrounding effects on the (hyper)polarizabilities are similar in the enol and keto forms, leading to optical contrasts very close to those of the isolated molecule. In contrast, an enhancement of the second-order susceptibility is observed in the keto form of 4P, leading to a large π(2)(K)/π(2)(E) contrast. Moreover, the π(2)(4A)/π(2)(4P) ratio for the most stable enol forms is obtained to be in good agreement with previous experimental investigations, which supports the reliability of the computational procedure. © 2011 American Chemical Society.

  2. Microwave spectroscopic and theoretical investigations of the strongly hydrogen bonded hexafluoroisopropanol···water complex. (United States)

    Shahi, A; Arunan, E


    This paper reports microwave spectroscopic and theoretical investigations on the interaction of water with hexafluoroisopropanol (HFIP). The HFIP monomer can exist in two conformations, antiperiplanar (AP) and synclinical (SC). The former is about 5 kJ mol(-1) more stable than the latter. Theoretical calculations predicted three potential minima for the complex, two having AP and one having SC conformations. Though, the binding energy for the HFIP(SC)···H2O turned out to be larger than that for the other two conformers having HFIP in the AP form, the global minimum for the complex in the potential energy hypersurface had HFIP in the AP form. Experimental rotational constants for four isotopologues measured using a pulsed nozzle Fourier transform microwave spectrometer, correspond to the global minimum in the potential energy hypersurface. The structural parameters and the internal dynamics of the complex could be determined from the rotational spectra of the four isotopologues. The global minimum has the HFIP(AP) as a hydrogen bond donor forming a strong hydrogen bond with H2O. To characterize the strength of the bonding and to probe the other interactions within the complex, atoms in molecules, non-covalent interaction index and natural bond orbital theoretical analyses have been performed.

  3. Theoretical and Experimental Investigation of the Nonlinear Behavior of an Electrostatically Actuated In-Plane MEMS Arch

    KAUST Repository

    Ramini, Abdallah


    We present theoretical and experimental investigation of the nonlinear behavior of a clamped-clamped in-plane MEMS arch when excited by a DC electrostatic load superimposed to an AC harmonic load. Experimentally, a case study of in-plane silicon micromachined arch is examined and its mechanical behavior is measured using optical techniques. An algorithm is developed to extract the various parameters, such as the induced axial force and the initial rise, needed to model the behavior of the arch. A softening spring behavior is observed when the excitation is close to the first resonance frequency due to the quadratic nonlinearity coming from the arch geometry and the electrostatic force. Also, a hardening spring behavior is observed when the excitation is close to the third (second symmetric) resonance frequency due to the cubic nonlinearity coming from mid-plane stretching. Dynamic snap-through behavior is also reported for larger range of electric loads. Theoretically, a multi-mode Galerkin reduced order model is utilized to simulate the arch behavior. General agreement is reported among the theoretical and experimental data.

  4. Investigation of Symphytum cordatum alkaloids by liquid-liquid partitioning, thin-layer chromatography and liquid chromatography-ion-trap mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mroczek, Tomasz [Department of Pharmacognosy with Medicinal Plants Laboratory, Medical University, 1 Chodzki St., 20-093 Lublin (Poland)]. E-mail:; Ndjoko-Ioset, Karine [Laboratoire de Pharmacognosie et Phytochimie, Ecole de Pharmacie Geneve-Lausanne, Universite de Geneve, Quai Ernest-Ansermet 30, CH-1211 Geneva 4 (Switzerland); Glowniak, Kazimierz [Department of Pharmacognosy with Medicinal Plants Laboratory, Medical University, 1 Chodzki St., 20-093 Lublin (Poland); Mietkiewicz-Capala, Agnieszka [Department of Pharmacognosy with Medicinal Plants Laboratory, Medical University, 1 Chodzki St., 20-093 Lublin (Poland); Hostettmann, Kurt [Laboratoire de Pharmacognosie et Phytochimie, Ecole de Pharmacie Geneve-Lausanne, Universite de Geneve, Quai Ernest-Ansermet 30, CH-1211 Geneva 4 (Switzerland)


    From the alkalised crude extract of Symphytum cordatum (L.) W.K. roots, pyrrolizidine alkaloids (PAs) were extracted as free tertiary bases and polar N-oxides in a merely one-step liquid-liquid partitioning (LLP) in separation funnel and subsequently pre-fractionated by preparative multiple-development (MD) thin-layer chromatography (TLC) on silica gel plates. In this way three alkaloid fractions of different polarities and retention on silica gel plates were obtained as: the most polar N-oxides of the highest retention, the tertiary bases of medium retention, and diesterified N-oxides of the lowest retention. The former fraction was reduced into free bases by sodium hydrosulfite and purified by LLP on Extrelut-NT3 cartridge. It was further analysed together with the two other fractions by high-performance liquid chromatography (HPLC)-ion-trap mass spectrometry with atmospheric pressure chemical ionization (APCI) interface on XTerra C{sub 18} column using a gradient elution. Based on MS {sup n} spectra, 18 various alkaloids have been tentatively determined for the first time in this plant as the following types of structure: echimidine-N-oxide (three diasteroisomers), 7-sarracinyl-9-viridiflorylretronecine (two diasteroisomers), echimidine (two diasteroisomers), lycopsamine (two diasteroisomers), dihydroechinatine-N-oxide, dihydroheliospathuline-N-oxide, lycopsamine-N-oxide (three diasteroisomers), 7-acetyllycopsamine-N-oxide, symphytine-N-oxide (two diasteroisomers) and 2'',3''-epoxyechiumine-N-oxide.

  5. Defect-induced Raman spectroscopy in single-layer graphene with boron and nitrogen substitutional defects by theoretical investigation (United States)

    Jiang, Jie; Pachter, Ruth; Islam, Ahmad E.; Maruyama, Benji; Boeckl, John J.


    Although advances in heteroatom incorporation into the single-layer graphene lattice resulted in films with large carrier densities, careful characterization by Raman spectroscopy is important for assessment of the material's quality. We investigated theoretically I(D)/I(D‧) Raman intensity ratios induced by B- and N- substitutional doping, demonstrated to be consistent with measurements. Calculated Fermi level shifts showed that for a moderate doping density results are comparable to electrolyte gating, while analytical analysis of the electron-defect scattering provided insight into changes of cross-sections. Effects of doping density on the D band intensity and broadening were quantified, and will assist in graphene characterization.

  6. Experimental and theoretical investigations on the singularity of the intensity factor of the current in high temperature superconductors (United States)

    Zhang, Xingyi; Huang, Yi; Zhou, Jun; Zhou, Youhe


    This paper presents experimental and analytical investigations into the distribution of current around a through-edge crack located in an infinitely long cylindrical high temperature superconductor (HTS) on the basis of the Bean model. Current distributions around the crack in the HTS without deformation are obtained by a simple conformal mapping. It is shown that the current is singular at the tip of the crack. An intensity factor of the current is introduced to characterize the singularity, the order of which is equal to -1. Additionally, an experimental verification according to the trapped field distributions around the crack is carried out, and the experimental results show little difference with the theoretical analysis.

  7. Crystal structure, NMR and theoretical investigations on 2-( o-hydroxy-anilino)-1,4-napthoquinone (United States)

    Feizi, Nourollah; Pinjari, Rahul V.; Gejji, Shridhar P.; Sayyed, Fareed B.; Gonnade, Rajesh; Rane, Sandhya Y.


    Crystal structure, 1H NMR and cyclic voltammetric investigations of 2-( o-hydroxy-anilino)-1,4-napthoquinone (HAN), resulting from coupling of aminophenol with 2-hydroxy-1,4-napthoquinone, have been carried out. X-ray structure reveals that the HAN ligand crystallizes in orthorhombic space group Pca2 1 with Z = 4, forming a chain via inter-molecular O2⋯H1A sbnd O1 and C15 sbnd H15⋯O3 interactions. Both 1H NMR and cyclic voltammetry experiments suggest the titled ligand is associated and exists as dimer in d6-DMSO while the monomer has been predicted in CDCl 3 solution. Density functional calculations can be utilized to gauge the strength of hydrogen-bonded interactions from the 1H chemical shifts in the NMR spectra. Self-consistent reaction field (SCRF) calculations further support the inferences drawn from cyclic voltammetry experiments.

  8. Solvent effect on the vibrational spectrum of Michler's ketone. Experimental and theoretical investigations. (United States)

    Sowula, Marta; Misiaszek, Tomasz; Bartkowiak, Wojciech


    We examined solvent effect on the IR and Raman spectra of MK in several solvents of different polarity and proticity, for understanding of intermolecular interactions, focusing on solvent effect in detail. It has been found that change of solvent polarity has an ambiguous influence on solvatochromism of MK. We have observed that not only vibrations of carbonyl group are affected by the solvent polarity, but also mode ν(CN) and ν(CC) in IR and Raman spectra of MK. Experimental investigations have been supported by the quantum-mechanical computations to gain more insight into the solvatochromic behavior of Michler's ketone. Calculations have been carried using Kohn-Sham formulation of Density Functional Theory (DFT) and the Polarizable Continuum Model (PCM) was employed to account for solute solvent interactions.

  9. X-band Dielectric Loaded Rf Driven Accelerator Structures Theoretical And Experimental Investigations

    CERN Document Server

    Zou, P


    An important area of application of high-power radio frequency (RF) and microwave sources is particle acceleration. A major challenge for the current worldwide research and development effort in linear accelerator is the search for a compact and affordable very-high-energy accelerator technology for the next generation supercolliders. It has been recognized for sometime that dielectric loaded accelerator structures are attractive candidates for the next generation very-high-energy linear accelerators, because they possess several distinct advantages over conventional metallic iris- loaded accelerator structures. However, some fundamental issues, such as RF breakdown in the dielectric, Joule heating, and vacuum properties of dielectric materials, are still the subjects of intense investigation, requiring the validation by experiments conducted at high power levels. An X-band traveling-wave accelerator based on dielectric-lined waveguide has been designed and constructed. Numerical calculation, bench measuremen...

  10. An experimental and theoretical investigation on torrefaction of a large wet wood particle. (United States)

    Basu, Prabir; Sadhukhan, Anup Kumar; Gupta, Parthapratim; Rao, Shailendra; Dhungana, Alok; Acharya, Bishnu


    A competitive kinetic scheme representing primary and secondary reactions is proposed for torrefaction of large wet wood particles. Drying and diffusive, convective and radiative mode of heat transfer is considered including particle shrinking during torrefaction. The model prediction compares well with the experimental results of both mass fraction residue and temperature profiles for biomass particles. The effect of temperature, residence time and particle size on torrefaction of cylindrical wood particles is investigated through model simulations. For large biomass particles heat transfer is identified as one of the controlling factor for torrefaction. The optimum torrefaction temperature, residence time and particle size are identified. The model may thus be integrated with CFD analysis to estimate the performance of an existing torrefier for a given feedstock. The performance analysis may also provide useful insight for design and development of an efficient torrefier.

  11. A spectroscopic and theoretical investigation of the proton-transfer laser. [Fisetin and 3-hydroxyflavone

    Energy Technology Data Exchange (ETDEWEB)

    Parthenopoulos, D.A.


    The lasing characteristics and the spectroscopy of intramolecular proton-transfer molecules were investigated in nonpolar and polar solvents. In addition, molecular orbital calculations on intramolecular proton-transfer molecules were performed. The efficient generation of coherent stimulated emission from 3-hydroxyflavone (3-HF) and fisetin, two molecules that exhibit intramolecular proton transfer was shown. Amplified spontaneous emission from 3-HF is achieved in polar aprotic and moderately protic solvents. The observed shifts of the tautomer fluorescence are attributed to hydrogen bonding interactions with the solvent. In contrast, 3-hydroxychromone does not exhibit amplified spontaneous emission in various solvents and concentrations. Picosecond transient absorption experiments reveal the existence of absorption bands overlapping the emission, which leads to high-loss terms in the gain equation.

  12. Detailed theoretical investigation of excited-state intramolecular proton transfer mechanism of a new chromophore II (United States)

    Cui, Yanling; Li, Yafei; Dai, Yumei; Verpoort, Francis; Song, Peng; Xia, Lixin


    In the present work, TDDFT has been used to investigate the excited state intramolecular proton transfer (ESIPT) mechanism of a new chromophore II [Sensors and Actuators B: Chemical. 202 (2014) 1190]. The calculated absorption and fluorescence spectra agree well with experimental results. In addition, two types of II configurations are found in the first excited state (S1), which can be ascribed to the ESIPT reaction. Based on analysis of the calculated infrared (IR) spectra of O-H stretching vibration as well as the hydrogen bonding energies, the strengthening of the hydrogen bond in the S1 state has been confirmed. The frontier molecular orbitals (MOs), Hirshfeld charge distribution and the Natural bond orbital (NBO) have also been analyzed, which displays the tendency of the ESIPT process. Finally, potential energy curves of the S0 and S1 states were constructed, demonstrating that the ESIPT reaction can be facilitated based on the photo-excitation.

  13. Theoretical and experimental investigation of fluid rheology effects on modulated ultrasound propagation. (United States)

    Özkök, Okan; Uludag, Yusuf


    A mathematical model is developed and presented to capture the effect of viscoelastic nature of a material on modulated ultrasound (US) pulses. The model is established by considering perturbation of material elements subject to modulated US pulses and by introducing the exponential relaxation of the perturbed fluid elements with a spectrum of time constants. Both the model and experimental findings revealed that consecutive perturbation of a material via the modulated US pulses enabled to probe the relaxation times of similar order of magnitudes to the frequency of the US modulation while filtering out the impact of other relaxation times on the US measurement. The US experimental results were verified by those of a conventional rheometer. Hence carrying out measurements at different US modulation frequencies in the Hz ranges seems to allow one to obtain the relaxation time spectrum of the investigated material in the time scales of milliseconds to seconds.

  14. Experimental and theoretical investigation of semiconductor optical amplifier (SOA) based all-optical switches

    DEFF Research Database (Denmark)

    Nielsen, Mads Lønstrup


    This thesis analyzes semiconductor optical amplifier (SOA) based all-optical switches experimentally and through numerical simulations. These devices are candidates for optical signal processing functionalities such as wavelength conversion, regeneration, and logic processing in future transparent...... optical networks. The factors governing the modulation bandwidth of SOAs are determined, and schemes for reducing detrimental patterning effects are discussed. Three types of SOA-based switches are investigated numerically: so-called standardmode and differential-mode switches, and the filtering assisted...... switch. Differential -mode switches are shown to eliminate one contribution to the patterning effects, referred to as the linear patterning. This enables operation at bitrates far beyond the limit set by the carrier lifetime, but ultimately a saturation-induced patterning effect, nonlinear patterning...

  15. Theoretical Investigation of Optical WDM Network Performance in the Presence of FWM and ASE Noise (United States)

    Iyer, Sridhar; Joy, Ambily


    In this article, for an optical star wavelength division multiplexing (WDM) network, with quality factor (Q-factor) as performance metric, we investigate the performance degradation due to the combined effects of four-wave mixing (FWM) and amplified spontaneous emission (ASE) noise. A mathematical model is developed, and the simulations are performed based on the optical frequency grid defined by the ITU-T Recommendation G.692. Further, the analysis is conducted for the optical fibers that are ITU-T compliant viz. G.652, G. 652D, G. 653, G. 654 and G.655. The simulation results show that, compared to the other fiber types, performance of the G. 652D and G.652 fibers is the "best", thus justifying the preferred use of fibers with high dispersion and effective area values. The simulation results also highlight that with the use of a fiber having low dispersion and effective area value, it may not be possible to obtain the desired performance.

  16. Theoretical Investigation of Uniform and Non-uniform Penetrable Sphere Fluid

    Institute of Scientific and Technical Information of China (English)

    ZHOU Shi-Qi


    A bridge function approximation is proposed for a single-component fluid consisting of penetrable sphere interacting via a potential that remains finite and constant for center-center distance smaller than the particle diameter and is zero otherwise. The radial distribution function from the Ornstein-Zernike integral equation combined with the present bridge function approximation is in satisfactory agreement with the corresponding simulation data for all of the investigated state points. The presently calculated excess Helmholtz free energy respectively based on virial route and compressibility route is highly self-consistent, and is in very good agreement with simulational results for the case of low temperatures. The present bridge function approximation, combined with the bridge density functional approximation,can reproduce very accurately density profiles of the penetrable sphere fluid confined in a hard spherical cavity for all the cases where simulational results are available.

  17. Theoretical Investigation on the Adsorption of Ag+ and Hydrated Ag+ Cations on Clean Si(111)Surface

    Institute of Scientific and Technical Information of China (English)

    SHENG Yong-Li; LI Meng-Hua; WANG Zhi-Guo; LIU Yong-Jun


    In this paper,the adsorption of Ag+ and hydrated Ag+ cations on clean Si(111)surface were investigated by using cluster(Gaussian 03)and periodic(DMol3)ab initio calculations.Si(111)surface was described with cluster models(Si14H17 and Si22H21)and a four-silicon layer slab with periodic boundary conditions.The effect of basis set superposition error(BSSE)was taken into account by applying the counterpoise correction.The calculated results indicated that the binding energies between hydrated Ag+ cations and clean Si(111)surface are large,suggesting a strong interaction between hydrated Ag+ cations and the semiconductor surface.With the increase of number,water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Ag+ cation.The Ag+ cation in aqueous solution will safely attach to the clean Si(111)surface.


    Institute of Scientific and Technical Information of China (English)

    B.W. Zhang; Z.M. Ren; Y.B. Zhong; K. Deng; K.D. Xu


    The electromagnetic field under applied AC and DC current in round and rectangularpipe was systematically investigated, then a concept of "equivalent current density"was proposed for evaluating the inhomogeneous electromagnetic pinch force, and themono-component removal efficiency and the overall removal efficiency of inclusionwere formulated. It is founded that flat pipe is superior to round pipe for the electro-magnetic removal of inclusion, and DC current can get a higher removal efficiencythan AC current due to absence of skin phenomenon. Under usual condition, a re-moval efficiency of 52% for 10μm inclusion or more than 92% for 20μm inclusioncan be achieved by imposing a current density of 3× 106A/m2 in a fiat pipe.

  19. Use of vector diffraction theory in theoretical and experimental investigation of SNOM tips (United States)

    Voznesensky, Nikolay B.; Veiko, Vadim P.


    An approach to the optical investigation of probes for scanning near-field optical microscopes (SNOM tips) and recognition of their near-field parameters by far-field measurements is considered. The comparison of approximate calculations of vector light field diffracted by a subwavelength aperture with more rigorous calculations of the light field passing through tapered end of a SNOM tip is presented. A numerical iterative procedure of the SNOM tip aperture reconstruction by the analytical continuation of the emerging light Fourier spectrum is presented. The approach is based on the use of plane waves covering a wide range of spatial frequencies. The results of experimental measurements and far-field data treatment with the definition of a subwavelength aperture are discussed.

  20. Theoretical investigation of OCN{sup -} adsorption onto boron nitride nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Soltani, Alireza, E-mail: [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Ahmadian, Nasim [Department of Chemistry, Qaemshahr Branch, Islamic Azad University, Qaemshar (Iran, Islamic Republic of); Amirazami, Abolfazl [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Masoodi, Anis [Young Researchers Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Lemeski, E. Tazikeh; Moradi, Ali Varasteh [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of)


    Highlights: Black-Right-Pointing-Pointer Adsorption behavior of OCN{sup -} on (6, 0) and (8, 0) BNNTs based on density functional theory. Black-Right-Pointing-Pointer OCN{sup -} is strongly bound to BNNTs in corresponding configurations. Black-Right-Pointing-Pointer The effect of the OCN{sup -} adsorption on the geometries and electronic properties of related BNNTs is investigated. Black-Right-Pointing-Pointer BNNTs is suggested as superior sensor for OCN{sup -} comparing with CNTs. - Abstract: First-principles calculations based on density functional theory (DFT) method are used to investigate the adsorption properties of OCN{sup -} on H-capped zigzag and armchair single-walled BN nanotubes (BNNTs). The results indicate that OCN{sup -} is strongly bound to the outer surface of zigzag (6, 0) BNNTs in comparison with armchair (5, 5) BNNT. Binding energy and equilibrium distance corresponding to the most stable configuration are found to be -486.79 kJ mol{sup -1} and 1.526 Angstrom-Sign , respectively being typical for the chemisorptions. Energy gap, dipole moment, natural atomic orbital occupancies and global indices for most stable configuration are calculated. Furthermore, the effect of the OCN{sup -} adsorption on the geometries and electronic properties of related BNNT is also studied. The calculated density of states (DOS) reveals that there is a significant orbital hybridization between two species in adsorption process being an evidence of strong interaction. Therefore, one can conclude that BNNTs play an important role as suitable sensor.

  1. Theoretical and experimental investigation of thermohydrologic processes in a partially saturated, fractured porous medium

    Energy Technology Data Exchange (ETDEWEB)

    Green, R.T.; Manteufel, R.D. [Nuclear Regulatory Commission, Washington, DC (United States). Div. of Regulatory Applications; Dodge, F.T.; Svedeman, S.J. [Southwest Research Inst., San Antonio, TX (United States). Center for Nuclear Waste Regulatory Analyses


    The performance of a geologic repository for high-level nuclear waste will be influenced to a large degree by thermohydrologic phenomena created by the emplacement of heat-generating radioactive waste. The importance of these phenomena is manifest in that they can greatly affect the movement of moisture and the resulting transport of radionuclides from the repository. Thus, these phenomena must be well understood prior to a definitive assessment of a potential repository site. An investigation has been undertaken along three separate avenues of analysis: (i) laboratory experiments, (ii) mathematical models, and (iii) similitude analysis. A summary of accomplishments to date is as follows. (1) A review of the literature on the theory of heat and mass transfer in partially saturated porous medium. (2) A development of the governing conservation and constitutive equations. (3) A development of a dimensionless form of the governing equations. (4) A numerical study of the importance and sensitivity of flow to a set of dimensionless groups. (5) A survey and evaluation of experimental measurement techniques. (6) Execution of laboratory experiments of nonisothermal flow in a porous medium with a simulated fracture.

  2. Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

    KAUST Repository

    de Ruiter, J. M.


    One of the key challenges in designing light-driven artificial photosynthesis devices is the optimization of the catalytic water oxidation process. For this optimization it is crucial to establish the catalytic mechanism and the intermediates of the catalytic cycle, yet a full description is often difficult to obtain using only experimental data. Here we consider a series of mononuclear ruthenium water oxidation catalysts of the form [Ru(cy)(L)(H2O)](2+) (cy = p-cymene, L = 2,2\\'-bipyridine and its derivatives). The proposed catalytic cycle and intermediates are examined using density functional theory (DFT), radiation chemistry, spectroscopic techniques, and electrochemistry to establish the water oxidation mechanism. The stability of the catalyst is investigated using online electrochemical mass spectrometry (OLEMS). The comparison between the calculated absorption spectra of the proposed intermediates with experimental spectra, as well as free energy calculations with electrochemical data, provides strong evidence for the proposed pathway: a water oxidation catalytic cycle involving four proton-coupled electron transfer (PCET) steps. The thermodynamic bottleneck is identified as the third PCET step, which involves O-O bond formation. The good agreement between the optical and thermodynamic data and DFT predictions further confirms the general applicability of this methodology as a powerful tool in the characterization of water oxidation catalysts and for the interpretation of experimental observables.

  3. Theoretical investigation of structural, energetic and electronic properties of titanate pyrochlores (United States)

    Xiao, H. Y.; Wang, L. M.; Zu, X. T.; Lian, Jie; Ewing, Rodney C.


    Ab initio total energy calculations using the plane-wave pseudopotential method based on density functional theory were carried out to investigate the structural, energetic and electronic properties of A2Ti2O7 (A = La, Gd and Yb) pyrochlores. It turned out that the formation energies of antisite defects are not linearly dependent on the ratio of the cation radii, and, for the three compositions, the cation antisite formation energy is largest for Gd2Ti2O7 pyrochlore. It was indicated that Gd2Ti2O7 compound is the least likely to form defect fluorite structure, which gives rise to the least resistance to radiation-induced amorphization. DOS analysis showed that stronger interaction exists in the Gd2Ti2O7 compound, and its electronic structure is very different from that of La2Ti2O7 and Yb2Ti2O7. Our calculations suggested that the electronic structure of the A cation and bond type should be taken into account when explaining the response behavior of A2Ti2O7 (A = La, Gd, Yb) pyrochlores to ion irradiation-induced amorphization.

  4. Experimental and Theoretical Investigation of Multispecies Oral Biofilm Resistance to Chlorhexidine Treatment (United States)

    Shen, Ya; Zhao, Jia; de La Fuente-Núñez, César; Wang, Zhejun; Hancock, Robert E. W.; Roberts, Clive R.; Ma, Jingzhi; Li, Jun; Haapasalo, Markus; Wang, Qi


    We investigate recovery of multispecies oral biofilms following chlorhexidine gluconate (CHX) and CHX with surface modifiers (CHX-Plus) treatment. Specifically, we examine the percentage of viable bacteria in the biofilms following their exposure to CHX and CHX-Plus for 1, 3, and 10 minutes, respectively. Before antimicrobial treatment, the biofilms are allowed to grow for three weeks. We find that (a). CHX-Plus kills bacteria in biofilms more effectively than the regular 2% CHX does, (b). cell continues to be killed for up to one week after exposure to the CHX solutions, (c). the biofilms start to recover after two weeks, the percentage of the viable bacteria recovers in the 1 and 3 minutes treatment groups but not in the 10 minutes treatment group after five weeks, and the biofilms fully return to the pretreatment levels after eight weeks. To understand the mechanism, a mathematical model for multiple bacterial phenotypes is developed, adopting the notion that bacterial persisters exist in the biofilms together with regulatory quorum sensing molecules and growth factor proteins. The model reveals the crucial role played by the persisters, quorum sensing molecules, and growth factors in biofilm recovery, accurately predicting the viable bacterial population after CHX treatment.

  5. Investigations on Synperiplanar and Antiperiplanar Isomers of Losartan: Theoretical and Experimental NMR Studies. (United States)

    Kujawski, Jacek; Czaja, Kornelia; Ratajczak, Tomasz; Jodłowska, Elżbieta; Chmielewski, Marcin K


    Losartan inhibits the renin-angiotensin-aldosterone system by blocking the angiotensin II receptor. It is commonly used in cardiovascular diseases, such as hypertension. Several publications applied the ab initio and density functional theory methods to investigate the molecule of losartan. Only in one of them were the nuclear magnetic resonance spectra calculations carried out, and their results were correlated with the experimental values. The authors focused their attention on calculations of the anion form of losartan, taking into consideration both its synperiplanar and antiperiplanar configurations. Coefficients of determination and mean absolute deviation parameters were calculated for the experimental and calculated chemical shifts for every used basis set. They showed a noticeably stronger correlation for the anti-isomers than for the syn-isomers. Moreover, the solvation model increased the value of this parameter. The results of calculations confirmed that an anti-conformation of the analyte seems to be the preferred one, and such an orientation might be most potent within the receptor cavity, which is in agreement with the results of previous studies.

  6. Experimental and theoretical investigation of [Al(PCr)(H2O)] complex in aqueous solution (United States)

    Tenório, Thaís; Lopes, Damiana C. N.; Silva, Andréa M.; Ramos, Joanna Maria; Buarque, Camilla D.


    Phosphocreatine is a phosphorylated creatine molecule synthesized in the liver and transported to muscle cells where it is used for the temporary storage of energy. In Alzheimer's disease, the capture of glucose by cells is impaired, which negatively affects the Krebs cycle, leading to problems with the generation of phosphocreatine. Furthermore, the creatine-phosphocreatine system, regulated by creatine kinase, is affected in the brains of Alzheimer's disease patients. Aluminum ions are associated with Alzheimer's disease. Al(III) decreases cell viability and increases the fluidity of the plasma membrane, profoundly altering cell morphology. In this study, one of the complexes formed by Al(III) and phosphocreatine in aqueous solution was investigated by potentiometry, 31P and 27Al NMR, Raman spectroscopy and density functional theory (DFT) calculations. The log KAlPCr value was 11.37 ± 0.03. Phosphocreatine should act as a tridentate ligand in this complex. The 27Al NMR peak at 48.92 ppm indicated a tetrahedral molecule. The fourth position in the arrangement was occupied by a coordinated water molecule. Raman spectroscopy, 31P NMR and DFT calculations (DFT:B3LYP/6-311++G**) indicated that the donor atoms are oxygen in the phosphate group, the nitrogen of the guanidine group and the oxygen of the carboxylate group. Mulliken charges, NBO charges, frontier molecular orbitals, electrostatic potential contour surfaces and mapped electrostatic potential were also examined.

  7. Theoretical Investigation of Detailed Thermodynamic Character of Possible Difunctional Adducts Model

    Institute of Scientific and Technical Information of China (English)

    CHANG Guan-Ru; ZHOU Li-Xin; CHEN Dong


    The B3LYP/6-31G* level of theory was used to optimize trans-[Pt(NH3)(Am)G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guanine sites of DNA as the ultimate target of platinum anticancer drugs. Bond dissociating energy and stability energy of complexes are chosen to study detailedly ther- modynamic character of possible difunctional adducts model. In order to investigate the influence of a polarizable environment on the energy of the Pt-L bond formation, we adopt a new bonding energy formula brought forward by Lippard and his coworkers: ΔH(Sol) = ΔH(SCF) + ΔG(Solv), which is quite appropriate to compare with what is found in experimental studies. Our calculated results demonstrate that N-containing ligands are more favored in view of thermodynamics both in gas phrase and in solution. However, it is worthly to be noted that addition of solvation free energies result in moderate correction of bonding energy in relative ordering, and the largest ones both present in imidazole ligand, not in guanine ligand. Finally, the nature of bond is analyzed in terms of partial charges distribution based on NBO population.

  8. A theoretical investigation on influences of slab tracks on vertical dynamic responses of railway viaducts (United States)

    Shi, Li; Cai, Yuanqiang; Wang, Peng; Sun, Honglei


    A railway viaduct model consisting of infinite spans of elastically-supported girders carrying a slab track of infinite length is established to investigate the influence of the slabs on the vertical dynamic response of the viaduct, when a moving harmonic point load or a moving sprung wheel is applied. The infinite rail, the discontinuous slabs and girders of identical span lengths are idealized as Euler-Bernoulli beams. The rail fasteners, the cushion layer beneath the slab and the elastic bearings at the girder supports are represented by discretely distributed springs of hysteretic damping. Due to the repetitive nature of the girders, the model can be divided into periodic three-beam units by the span length of the girder, and then solved analytically in the frequency domain using the property of periodic structure. Besides the first natural frequency of the girder with elastic bearings, it is found that the resonance frequency of the slab on the cushion layer has a significant influence on the dynamic response of the track and the girder. Parametric excitations due to the moving wheel periodically passing the discontinuous slabs contribute significantly to the wheel/rail interactions.

  9. Theoretical and experimental investigation on giant magnetoresistive materials with amorphous ferromagnetic layer

    Institute of Scientific and Technical Information of China (English)

    WEN Qi-ye; ZHANG Huai-wu; SONG Yuan-qiang; JIANG Xiang-dong


    Pseudo-spin-valve (PSV) sandwiches using amorphous CoNbZr alloy as soft magnetic layer were fabricated by magnetron sputtering. The giant magnetoresistance (GMR) and its dependence on the thickness of magnetic layer were investigated. Anti-parallel magnetization alignments were observed in the samples with very thin CoNbZr thickness (2-4 nm) and a maximum GMR ratio of 6.5% was obtained. The Camley-Barnas semiclassical model was extended for amorphous layer based magnetic sandwiches by considering that the mixed layers exist between the ferromagnetic and nonmagnetic layer. The calculated results agree with the experimental results very well,indicating that the new model gives a more realistic picture of the physical processes that take place in the magnetic sandwiches. Moreover,the calculated results for amorphous sandwiches also clarify that the occurrence of maximum GMR at very small thickness of amorphous layer is ascribed to the short mean-free-path in amorphous materials.


    Energy Technology Data Exchange (ETDEWEB)

    Barashev, Alexander V [ORNL; Golubov, Stanislav I [ORNL; Stoller, Roger E [ORNL


    This work is based on our reaction-diffusion model of radiation growth of Zr-based materials proposed recently in [1]. In [1], the equations for the strain rates in unloaded pure crystal under cascade damage conditions of, e.g., neutron or heavy-ion irradiation were derived as functions of dislocation densities, which include contributions from dislocation loops, and spatial distribution of their Burgers vectors. The model takes into account the intra-cascade clustering of self-interstitial atoms and their one-dimensional diffusion; explains the growth stages, including the break-away growth of pre-annealed samples; and accounts for some striking observations, such as of negative strain in prismatic direction, and co-existence of vacancy- and interstitial-type prismatic loops. In this report, the change of dislocation densities due to accumulation of sessile dislocation loops is taken into account explicitly to investigate the dose dependence of radiation growth. The dose dependence of climb rates of dislocations is calculated, which is important for the climb-induced glide model of radiation creep. The results of fitting the model to available experimental data and some numerical calculations of the strain behavior of Zr for different initial dislocation structures are presented and discussed. The computer code RIMD-ZR.V1 (Radiation Induced Microstructure and Deformation of Zr) developed is described and attached to this report.

  11. Theoretical Investigation of the Optical Spectra of Organic Compounds in Natural Surrounding (United States)

    Pomogaev, V. A.; Artyukhov, V. Ya.


    The hybrid multiscale approximation based on molecular dynamics, quantum mechanics, and statistical theory is used to generate profiles of electronic vibrational absorption and fluorescence bands of some organic compounds and biological objects whose photophysical properties specifically depend on external conditions. A temperature dependence of the spectrum width and intensity of transition to the long-wavelength band of benzene surrounded by cyclohexane molecules is demonstrated. Statistical broadband absorption spectra for estradiol in ethanol, hexane, and dimethyl sulfoxide have been obtained and analyzed at room temperature together with a wide spectrum of transitions to numerous excited states of Trp-cage miniprotein. The absorption and emission spectra of 9-cyan anthracene have been generated under various thermodynamic conditions. This allows changes in the spectral profile with increasing temperatures and pressure to be detected. A dependence of the tryptophan spectra on the protein microsurrounding is investigated. The possibility of charge transfer from tryptophan residue to the eupatorin molecule trapped by human serum albumin is analyzed. Spectral properties and charge transfer from the excited donor to acceptor states are calculated using the polarizable embedding approach for modeling of surrounding protein structure.

  12. Experimental and theoretical investigation effect of flavonols antioxidants on DNA damage. (United States)

    Ensafi, Ali A; Heydari-Soureshjani, E; Jafari-Asl, M; Rezaei, B; Ghasemi, Jahan B; Aghaee, Elham


    A new electrochemical biosensor was developed to demonstrate the effect of Acridine Orange (AO) on DNA damage. Then, the biosensor was used to check the inhibitors effect of three flavonols antioxidants (myricetin, fisetin and kaempferol) on DNA damage. Acridine Orange (AO) was used as a damaging agent because it shows a high affinity to nucleic acid and stretch of the double helical structure of DNA. Decreasing on the oxidation signals of adenine and guanine (in the DNA) in the presence of AO were used as probes to study the antioxidants power, using DNA-modified screen printed graphene electrode (DNA/SPGE). The results of our study showed that the DNA-biosensor could be suitable biosensor to investigate the inhibitors ability of the flavonols antioxidants on the DNA damage. The linear dependency was detected in the two regions in the ranges of 1.0-15.0 and 15.0-500.0 pmol L(-1). The detection limit was found 0.5 pmol L(-1) and 0.6 pmol L(-1) for guanine and adenine, respectively. To confirm the electrochemical results, Uv-Vis and fluorescence spectroscopic methods were used too. Finally molecular dynamic (MD) simulation was performed on the structure of DNA in a water box to study any interaction between the antioxidant, AO and DNA.

  13. Theoretical investigation on the heats of formation and detonation performance in polydinitroaminocubanes. (United States)

    Chi, Weijie; Wang, Xiuyan; Li, Butong; Wu, Haishun


    A series of polydinitroaminocubanes have been designed computationally. We calculated the heats of formation, the detonation velocity (D) and detonation pressure (P) of the title compounds by density function theory (DFT) with 6-311 G** basis set. The relationship between the heats of formation and the molecular structures is discussed. The result shows that all cubane derivatives have high and positive heats of formation, which increase with increasing number of dinitroamino groups. The detonation performances of the title compound were estimated by Kamlet-Jacobs equation, and the result indicated that most cubane derivatives have good detonation performance over RDX (hexahydro-1,3,5-trinitro-1,3,5-trizine) and HMX (1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane). In addition, we also found that the heat of detonation (Q) is another very important impact in increasing detonation performance except density. The relative stabilities of the title compound are discussed in the terms of the calculated heats of formation, and the energy gaps between the frontier orbitals. The results have not only shown that these compounds may be used as high energy density compounds (HEDCs), but also provide some useful information for further investigation.

  14. Boron carbide nanoclusters as H2 and N2 gases nanosensors: theoretical investigation (United States)

    Fallahpour, F.; Gorgani, S. Soleimani; Nouraliei, M.


    Interactions between boron carbide nanoclusters (B16C16 and B24C24) and H2 and N2 molecules have been investigated using the structural and electronic properties of the adsorbate/cluster complexes derived from density functional theory. The adsorption energies of the most stable configurations have been calculated to be about -0.13, -0.66 eV for H2 and N2 adsorbed on the B16C16 surface and -1.05, -3.80 eV for H2 and N2 adsorbed on the B24C24 surface, respectively. Moreover, the interaction between H2 and the B16C16 has induced dramatic changes to the cluster electronic properties, so that the HOMO/LUMO gap of the cluster decreases to its original value. It has been shown that this phenomenon has led to an increment in the electrical conductivity of the cluster at a definite temperature. Thus, this work suggests that the B16C16 and B24C24 nano-cages function selectively as a gas sensor device for H2 and N2 molecules.

  15. Theoretical investigation of coherent synchrotron radiation induced microbunching instability in transport and recirculation arcs

    CERN Document Server

    Tsai, Cheng-Ying; Li, Rui; Tennant, Christopher


    The coherent synchrotron radiation (CSR) of a high brightness electron beam traversing a series of dipoles, such as recirculation or transport arcs, may lead to the microbunching instability. We extend and develop a semi-analytical approach of the CSR-induced microbunching instability for a general lattice, based on the previous formulation with 1-D CSR model [Phys. Rev. ST Accel. Beams 5, 064401 (2002)] and apply it to investigate the physical processes of microbunching amplification for two example transport arc lattices. We find that the microbunching instability in transport arcs has a distinguishing feature of multistage amplification (e.g, up to 6th stage for our example arcs in contrast to two stage amplification for a 3-dipole chicane). By further extending the concept of stage gain as proposed by Huang and Kim [Phys. Rev. ST Accel. Beams 5, 074401 (2002)], we developed a method to quantitatively characterize the microbunching amplification in terms of iterative or staged orders that allows the compar...

  16. Theoretical Investigation of Creeping Viscoelastic Flow Transition Around a Rotating Curved Pipe

    CERN Document Server

    Hamza, S E E


    The study of creeping motion of viscoelastic fluid around a rotating rigid torus is investigated. The analysis of the problem is performed using a second-order viscoelastic model. The study is carried out in terms of the bipolar toroidal system of coordinates where the toroid is rotating about its axis of symmetry (z-axis). The problem is solved within the frame of slow flow approximation. Therefore, all variables in the governing equations are expanded in a power series of angular velocity. A set of successive partial differential equations is obtained. The equations of motion governing the first and second-order are formulated and solved for the first-order only in this paper. However, the solution of the second-order equations will be the subject of a part two of this series of papers. Analytically, Laplace's equation is solved via the usual method of separation of variables. This method shows that, the solution is given in a form of infinite sums over Legendre functions of the first and second kinds. From...

  17. Theoretical investigation of hyperthermal reactions at the gas-liquid interface: O (3P) and squalane. (United States)

    Kim, Dongwook; Schatz, George C


    Hyperthermal collisions (5 eV) of ground-state atomic oxygen [O ((3)P)] with a liquid-saturated hydrocarbon, squalane (C(30)H(62)), have been studied using QM/MM hybrid "on-the-fly" direct dynamics. The surface structure of the liquid squalane is obtained from a classical molecular dynamics simulation using the OPLS-AA force field. The MSINDO semiempirical Hamiltonian is combined with OPLS-AA for the QM/MM calculations. In order to achieve a more consistent and efficient simulation of the collisions, we implemented a dynamic partitioning of the QM and MM atoms in which atoms are assigned to QM or MM regions based on their proximity to "seed" (open-shell) atoms that determine where bond making/breaking can occur. In addition, the number of seed atoms is allowed to increase or decrease as time evolves so that multiple reactive events can be described. The results show that H abstraction is the most important process for all incident angles, with H elimination, double H abstraction, and C-C bond cleavage also being important. A number of properties of these reactive channels, as well as inelastic nonreactive scattering, are investigated, including angular and translational energy distributions, the effect of incident collision angle, variation with depth of the reactive event within the liquid, with the reaction site on the hydrocarbon, and the effect of dynamics before and after reaction (direct reaction versus trapping reaction-desorption).

  18. Theoretical investigation of pressure drop in combined cyclone and fabric filter systems (United States)

    Dirgo, John A.; Cooper, Douglas W.

    Computer simulations were conducted to investigate potential pressure drop reductions obtainable by combining cyclones, as pre-collectors, with fabric filters. The Leith-Licht model was used to characterize cyclone emissions and the specific resistance ( K2) of the fabric filter dust cake was calculated from an empirical correlation. Several important dimensionless groups were identified and evaluated. One group, the product of the ratio of the dust cake specific resistances expected with and without the cyclone and the mass penetration of the cyclone, ( K2/ K2) Pn, indicates whether a pressure drop reduction is possible. A correlation was developed for this group as a function of the size properties of the inlet dust (particle mass median diameter and geometric standard deviation) and the cyclone particle cut diameter. Expressions were derived for the break-even time, the duration of filtration with the cyclone needed to show a pressure drop reduction in comparison with filtration without the cyclone. It is shown that in previously reported experiments and simulations indicating an advantage for the combined cyclone-fabric filter system, filtration cycles were typically longer than the break-even time; those showing no improvement typically had filtration times shorter than the break-even time.

  19. Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump. (United States)

    Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi


    The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products.

  20. Theoretical Investigation on the Solubilization in Water of Functionalized Single-Wall Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Michael Mananghaya


    Full Text Available An important technique to increase the solubility and reactivity of carbon nanotube is through functionalization. In this study, the effects of functionalization of some single-walled carbon nanotubes (SWCNTs were investigated with the aid of density functional theory. The SWCNT model used in the study consists of a finite, (5, 0 zigzag nanotube segment containing 60 C atoms with hydrogen atoms added to the dangling bonds of the perimeter carbons. There are three water-dispersible SWCNTs used in this study that were functionalized with (a formic acid, as a model of carboxylic acid, (b isophthalic acid, as a model aromatic dicarboxylic acid, and (c benzenesulfonic acid, as a model aromatic sulfonic acid. Binding energies of the organic radicals to the nanotubes are calculated, as well as the HOMO-LUMO gaps and dipole moments of both nanotubes and functionalized nanotubes. Binding was found out to be thermodynamically favorable. The functionalization increases the electrical dipole moments and results in an enhancement in the solubility of the nanotubes in water manifested through favorable changes in the free energies of solvation. This should lower the toxicity of nanotubes and improve their biocompatibility.

  1. Theoretical investigations of the interfacial sliding and buckling of graphene on a flexible substrate (United States)

    Cui, Zhen; Guo, Jian-Gang


    Two interfacial failure modes, shear sliding and buckling, of graphene on a flexible substrate subjected to uniaxial compression are investigated. The shear sliding starts at the edge region, and buckling starts at the middle region of graphene. Using shear-lag cohesive zone models and finite element (FE) simulations, the critical strain and maximum strain of graphene are predicted for the interfacial sliding failure. Then, the critical strain for the onset of buckling is derived via the theory of continuum mechanics with the van der Waals (vdW) interaction between graphene and the substrate surface taken into consideration. By comparison of the two critical failure strains and maximum strain of graphene, it is found that there exists a critical length of graphene. As the graphene length is larger than it, interfacial failure goes through four stages of development with increasing loading, including sliding and buckling. Conversely, the buckling of graphene will not occur. Finally, the influence of the interfacial adhesion energy and geometric size of graphene on the critical strains for interfacial sliding and buckling are discussed.

  2. Insertion of Group 12-16 Hydrides into NHCs: A Theoretical Investigation. (United States)

    Iversen, Kalon J; Dutton, Jason L; Wilson, David


    The endocyclic ring expansion of N-heterocyclic carbene (NHC) rings by transition metal (Group 12) and main group (Group 13-16) element hydrides has been investigated in a computational study. In addition to previously reported insertion reactivity with Si, B, Be and Zn, similar reactivity is predicted to be feasible for heavier group 13 elements (Al, Ga, In, Tl), with the reaction barriers for Al-Tl calculated to be lower than for boron. Insertion is not expected with group 15-16 element hydrides, as the initial adduct formation is thermodynamically unfavourable. The reaction pathway with group 12 hydrides is calculated to be more favourable with two NHCs rather than a single NHC (analogous to Be), however hydride ring insertion with metal dihydrides is not feasible, but rather a reduced NHC is thermodynamically favoured. For group 14, ring-insertion reactivity is predicted to be feasible with the heavier dihydrides. Trends in reactivity of element hydrides may be related to the protic or hydridic character of the element hydrides.

  3. Experimental and theoretical investigation of Cr1-xScxN solid solutions for thermoelectrics

    DEFF Research Database (Denmark)

    Kerdsongpanya, Sit; Sun, Bo; Eriksson, Fredrik


    . Here, we demonstrate an approach to tailor their thermoelectric properties by solid solutions. The trends in mixing thermodynamics and densities-of-states (DOS) of rocksalt-Cr1-xScxN solid solutions (0 ≤ x ≤ 1) are investigated by first-principles calculations, and Cr1-xScxN thin films are synthesized...... by magnetron sputtering. Pure CrN exhibits a high power factor, 1.7 × 10−3 W m−1 K−2 at 720 K, enabled by a high electron concentration thermally activated from N vacancies. Disordered rocksalt-Cr1-xScxN solid solutions are thermodynamically stable, and calculated DOS suggest the possibility for power......-factor improvement by Sc3d orbital delocalization on Cr3d electrons giving decreasing electrical resistivity, while localized Cr3d orbitals with a large DOS slope may yield an improved Seebeck coefficient. Sc-rich solid solutions show a large improvement in power factor compared to pure ScN, and all films have power...

  4. Theoretical investigation of the mechanism of tritiated methane dehydrogenation reaction using nickel-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Liang; Li, Jiamao; Deng, Bing; Yang, Yong; Wang, Heyi [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Li, Shuo, E-mail: [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Tan, Zhaoyi, E-mail: [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)


    Graphical abstract: - Highlights: • Four-step dehydrogenation of CT{sub 4} catalyzed by Ni to form Ni–C by releasing T{sub 2}. • The process of Ni + CT{sub 4} → NiCT{sub 2} + T{sub 2} is more achievable than that of NiCT{sub 2} → NiC + T{sub 2}. • TNiCT → T{sub 2}NiC step is the RDS with the rate constant of k = 2.8 × 10{sup 13} exp(−313,136/RT). • The hydrogen isotope effect value of k{sub H}/k{sub T} is 2.94, and k{sub D}/k{sub T} is 1.39. • CH{sub 4} and CD{sub 4} dehydrogenations are likely to occur, accompanied by the CT{sub 4} cracking. - Abstract: The mechanism of tritiated methane dehydrogenation reaction catalyzed by nickel-based catalyst was investigated in detail by density functional theory (DFT) at the B3LYP/[6-311++G(d, p), SDD] level. The computational results indicated that the dehydrogenation of tritiated methane is endothermic. The decomposition of tritiated methane catalyzed by Ni to form Ni-based carbon (Ni–C) after a four-step dehydrogenation companied with releasing tritium. After the first and second dehydrogenation steps, Ni + CT{sub 4} formed NiCT{sub 2}. After the third and fourth dehydrogenation steps, NiCT{sub 2} formed NiC. The first and second steps of dehydrogenation occurred on both the singlet and triplet states, and the lowest energy route is Ni + CT{sub 4} → {sup 1}COM → {sup 1}TS1 → {sup 3}IM1 → {sup 3}TS2 → {sup 3}IM2. The third and fourth steps of dehydrogenation occurred on both the singlet and quintet states, and the minimum energy reaction pathway appeared to be IM3 → {sup 1}TS4 → {sup 5}IM4 → {sup 5}TS5 → {sup 5}IM5 → {sup 5}pro + T{sub 2}. The fourth step of dehydrogenation TNiCT → T{sub 2}NiC was the rate-determining step of the entire reaction with the rate constant of k{sub 2} = 2.8 × 10{sup 13} exp(−313,136/RT) (in cm{sup 3} mol{sup −1} s{sup −1}), and its activation energy barrier was calculated to be 51.8 kcal/mol. The Ni-catalyzed CH{sub 4} and CD{sub 4} cracking

  5. Experimental and theoretical investigations of mercury adsorption on hematite (1-102) surfaces (United States)

    Jung, J.; Wilcox, J.; Jew, A. D.; Rupp, E. C.; Brown, G. E.


    Fly ash is a primary byproduct of the coal combustion process. The release of fly ash into the environment and its use in consumer products are public health concerns because of the presence of toxic trace metals and metalloids, such as mercury (Hg), selenium (Se), and arsenic (As), which may exist as components of fly ash, partition onto fly ash as it cools, or is lost to the environment through smoke stacks in a vapor phase. Therefore, it is important to understand the components of fly ash and their interaction with trace metals. In this study, calculations using density functional theory (DFT) were carried out in conjunction with experimental studies to investigate the interaction between Hg and hematite, an important mineral component of fly ash. Our experimental study, designed to simulate Hg sorption in a coal-fired power plant exhaust system, involved exposure of the fine fraction of bituminous coal fly ash (≤ 0.1 μm) to methane combustion flue gas, supplemented with SO2, NOx, HCl, and Hg in a packed-bed reactor. Sorption reaction products were characterized by synchrotron-based x-ray fluorescence mapping (s-XRF), x-ray diffraction (XRD), and extended x-ray absorption fine structure (EXAFS) spectroscopy. Preliminary s-XRF results showed that Hg in the sample is correlated with Fe, S, Cl, Br, and to a lesser extent with Se and As. From the XRD analysis, the dominant mineral phases detected were quartz, iron oxide (hematite), and various sulfate-bearing cements. Based on the experimental results, DFT studies were carried out to investigate the adsorption of Hg on hematite (α-Fe2O3) (1-102) surfaces. The two α-Fe2O3 (1-102) surfaces modeled consisted of two different surface terminations: (1) M2-clean, which corresponds to the oxygen terminated r-cut surface with the first layer of cations removed and no hydroxyl group and (2) M2-OH2-OH which has bihydroxylated top oxygen atoms and a second layer of hydroxylated oxygen atoms. These surface terminations

  6. Theoretical investigation of lead vapor adsorption on kaolinite surfaces with DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xinye [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Huang, Yaji, E-mail: [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Pan, Zhigang [College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009 (China); Wang, Yongxing; Liu, Changqi [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China)


    Highlights: • Al surface after dehydroxylation is active while Si surface is inert. • The active sites are the unsaturated Al atoms and O atoms losing H atom. • PbO is the most suitable species for adsorption. • Increasing the activities of Al atoms can enhance the performance of kaolinite. • Produce of amorphous silica is a potential path to enhance the performance of kaolinite. - Abstract: Kaolinite can be used as the in-furnace sorbent/additive to adsorb lead (Pb) vapor at high temperature. In this paper, the adsorptions of Pb atom, PbO molecule and PbCl{sub 2} molecule on kaolinie surfaces were investigated by density functional theory (DFT) calculation. Si surface is inert to Pb vapor adsorption while Al surfaces with dehydroxylation are active for the unsaturated Al atoms and the O atoms losing H atoms. The adsorption energy of PbO is much higher than that of Pb atom and PbCl{sub 2}. Considering the energy barriers, it is easy for PbO and PbCl{sub 2} to adsorb on Al surfaces but difficult to escape. The high energy barriers of de–HCl process cause the difficulties of PbCl{sub 2} to form PbO·Al{sub 2}O{sub 3}·2SiO{sub 2} with kaolinite. Considering the inertia of Si atoms and the activity of Al atoms after dehydroxylation, calcination, acid/alkali treatment and some other treatment aiming at amorphous silica producing and Al activity enhancement can be used as the modification measures to improve the performance of kaolinite as the in-furnace metal capture sorbent.

  7. An ab-initio theoretical investigation of the soft-magnetic properties of permalloys

    Energy Technology Data Exchange (ETDEWEB)

    Ostanin, S. [Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom); Staunton, J.B. [Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom)]. E-mail:; Razee, S.S.A. [Department of Physics, University of Kuwait, SAFAT 13060 (Kuwait); Ginatempo, B. [Dipartimento di Fisica and Unita INFM, Universita di Messina, Salita Sperone 31, I-98166 Messina (Italy); Bruno, Ezio [Dipartimento di Fisica and Unita INFM, Universita di Messina, Salita Sperone 31, I-98166 Messina (Italy)


    We study Ni{sub 80}Fe{sub 20}-based permalloys with the relativistic spin-polarized Korringa-Kohn-Rostoker electronic structure method. Treating the compositional disorder with the coherent potential approximation, we investigate how the magnetocrystalline anisotropy, K, and magnetostriction, {lambda}, of Ni-rich Ni-Fe alloys vary with the addition of small amounts of non-magnetic transition metals, Cu and Mo. From our calculations we follow the trends in K and {lambda} and find the compositions of Ni-Fe-Cu and Ni-Fe-Mo where both are near zero. These high permeability compositions of Ni-Fe-Cu and Ni-Fe-Mo match well with those discovered experimentally. We monitor the connection of the magnetic anisotropy with the number of minority spin electrons N{sub {down_arrow}}. By raising N{sub {down_arrow}} via artificially increasing the band-filling of Ni{sub 80}Fe{sub 20}, we are able to reproduce the key features that underpin the magnetic softening we find in the ternary alloys. The effect of band-filling on the dependence of magnetocrystalline anisotropy on atomic short-range order in Ni{sub 80}Fe{sub 20} is also studied. Our calculations, based on a static concentration wave theory, indicate that the susceptibility of the high permeability of the Ni-Fe-Cu and Ni-Fe-Mo alloys to their annealing conditions is also strongly dependent on the alloys' compositions. An ideal soft magnet appears from these calculations.

  8. Polymorphism in chloro derivatives of 1,4-naphthoquinone: Experiment and density functional theoretic investigations (United States)

    Chaudhari, Dinkar; Gejji, Shridhar P.; Lande, Dipali N.; Chakravarty, Debamitra; Salunke-Gawali, Sunita


    Molecular interactions underlying polymorphs of chlorine containing 1,4-naphthoquinone derivatives have been investigated by employing single crystal X-ray, 1H NMR, FTIR and electronic spectra experiments combined with density functional theory. Two polymorphs of 2,3-dichloro-1,4-naphthoquinone possessing (i) triclinic space group P-1(A1 and A3), and (ii) orthorhombic with Pb21a (A2) space group were obtained. The polymorph A3 has two molecules in its asymmetric unit which facilitate Csbnd H⋯O interactions engendeing polymeric planar sheets. The two polymorphs of 2-amino-3-chloro-1,4-naphthoquinone reveal monoclinic forms with Pc (B1) and C2/C (B2) space groups. A tetramer of B2 molecule possess Nsbnd H⋯O interactions. The polymorphs of 2-chloro-3-hydroxy-1,4-naphthoquinone crystallizes in monoclinic space groups Pc (C1) and Pn (C2). Polymeric chain of C2 molecules results via Osbnd H⋯O interactions and the chains further are connected through Csbnd H⋯Cl and π-π stacking interactions those arise from benzenoid and quinonoid centroid. Moreover A3 facilitates the dimer via the halogen bonding interactions. Furthermore hydrogen bonding renders stability to the dimer C2. On the other hand compound B2 does not favor dimer formation. These inferences based on experimental observations are rationalized through the use of the dispersion corrected M06-2x functional based density functional theory. Further time dependent density functional theory has been used to assign the electronic transitions in UV-visible spectra of A3, B2 and C2.

  9. Theoretical investigation of interaction between a rectangular plate and fractional viscoelastic foundation

    Institute of Scientific and Technical Information of China (English)

    Chengcheng Zhang; Honghu Zhu; Bin Shi; Linchao Liu


    The interaction between plates and foundations is a typical problem encountered in geotechnical en-gineering. The long-term plate performance is highly dependent on the rheological characteristics of ground soil. Compared with conventional linear rheology, the fractional calculus-based theory is a more powerful mathematical tool that can address this issue. This paper proposes a fractional Merchant model (FMM) to investigate the time-dependent behavior of a simply supported rectangular plate on visco-elastic foundation. The correspondence principle involving Laplace transforms was employed to derive the closed-form solutions of plate response under uniformly distributed load. The plate deflection, bending moment, and foundation reaction calculated using the FMM were compared with the results obtained from the analogous elastic model (EM) and the standard Merchant model (SMM). It is shown that the upper and lower bound solutions of the FMM can be determined using the EM. In addition, a parametric study was performed to examine the influences of the model parameters on the time-dependent behavior of the plateefoundation interaction problem. The results indicate that a small fractional differential order corresponds to a plate resting on a sandy soil foundation, while the fractional differential order value should be increased for a clayey soil foundation. The long-term performance of a foundation plate can be accurately simulated by varying the values of the fractional differential order and the viscosity coefficient. The observations from this study reveal that the proposed fractional model has the capability to capture the variation of plate deflection over many decades of time.

  10. Theoretical Investigation of Mechanisms for the Gas-Phase Unimolecular Decomposition of DMMP (United States)

    Yang, Li; Shroll, Robert M.; Zhang, Jiaxu; Lourderaj, U.; Hase, William L.


    All species involved in the multichannel decomposition of gas-phase dimethyl methylphosphonate (DMMP) were investigated by electronic structure calculations. Geometries for stationary structures along the reaction paths, were fully optimized with the MP2 method and the B3LYP and MPW1K DFT functionals, and the 6-31G*, 6-31++G**, and aug-cc-pVDZ basis sets. The geometries determined by the B3LYP and MPW1K functionals are in very good agreement with the MP2 values. Increasing the basis set size from 6-31G* to aug-cc-pVDZ does not significantly alter this result. Single point energy calculations were carried out with highly accurate but computationally more expensive CBS-QB3 theory. DMMP has three conformers, which lead to the four primary product channels, (O)P(CH2)(OCH3) + CH3OH, (O)P(CH3) (OCH3)(OH) + CH2, c-(O)P(CH3)OCH2 + CH3OH, and (O)P(CH3)(OCH3)(OCH) + H2. The first channel has the lowest energy barrier and is expected to be the most important pathway. It occurs via C-H and P-O bond cleavages accompanied by O-H bond formation. The other three channels have higher and similar energy barriers, and are expected to have smaller and similar rates. The product (O)P(CH3)(OCH3)(OCH) undergoes a secondary decomposition to form (OH)P(CH3)(OCH3) + CO.

  11. A theoretical and numerical investigation of travelling wave induction microfluidic pumping in a temperature gradient (United States)

    Liu, Weiyu; Ren, Yukun; Shao, Jinyou; Jiang, Hongyuan; Ding, Yucheng


    The phenomenon of induction electrohydrodynamics (EHD) has recently received great attention as a promising driving mechanism for microfluidic pumping due to its miniaturization capability. To obtain a high working efficiency of induction micropumps, a vertical temperature gradient can be imposed along the depth of a pump channel. A travelling wave (TW) potential signal propagating along an electrode array at the channel substrate interacts with this conductive heat flux, resulting in a local free charge distribution inside the bulk fluid. The induced charge wave lags behind the voltage wave in the spatial phase, and this out-of-phase polarization based pumping effect exhibits a single structural dispersion at charge relaxation frequency of the dielectric system. The classical model of electrothermal flow has always been used to numerically obtain the flow field of TW pumps, but the effect of its small temperature gradient approximation has rarely been investigated. In this study, an enhanced treatment for induction EHD modelling is developed, in which the deflection of potential contour lines caused by large temperature gradients is successfully characterized by an advection-diffusion equation, and a more accurate expression of electrothermal body force is derived and introduced to fluid dynamics as a source term of electrical origin. For the calculation of a repulsion-type induction micropump, although both models present similar results in a small thermal gradient, the enhanced one can provide more exact frequency-dependence of the pump performance and spatial distribution of electrostatic force as well as the resulting velocity profile in an excessive heat flux. Furthermore, a model extension for Joule heating induced TW pumping is also presented, and surprisingly matches the unexpected nonlinear fluid flow behaviour at higher conductivities as reported in a pioneering literature. These results can provide valuable insights into induction pumping of lab

  12. Theoretical investigation of interaction between a rectangular plate and fractional viscoelastic foundation

    Directory of Open Access Journals (Sweden)

    Chengcheng Zhang


    Full Text Available The interaction between plates and foundations is a typical problem encountered in geotechnical engineering. The long-term plate performance is highly dependent on the rheological characteristics of ground soil. Compared with conventional linear rheology, the fractional calculus-based theory is a more powerful mathematical tool that can address this issue. This paper proposes a fractional Merchant model (FMM to investigate the time-dependent behavior of a simply supported rectangular plate on viscoelastic foundation. The correspondence principle involving Laplace transforms was employed to derive the closed-form solutions of plate response under uniformly distributed load. The plate deflection, bending moment, and foundation reaction calculated using the FMM were compared with the results obtained from the analogous elastic model (EM and the standard Merchant model (SMM. It is shown that the upper and lower bound solutions of the FMM can be determined using the EM. In addition, a parametric study was performed to examine the influences of the model parameters on the time-dependent behavior of the plate–foundation interaction problem. The results indicate that a small fractional differential order corresponds to a plate resting on a sandy soil foundation, while the fractional differential order value should be increased for a clayey soil foundation. The long-term performance of a foundation plate can be accurately simulated by varying the values of the fractional differential order and the viscosity coefficient. The observations from this study reveal that the proposed fractional model has the capability to capture the variation of plate deflection over many decades of time.

  13. Ionic liquids as stationary phases in gas chromatography--an LSER investigation of six commercial phases and some applications. (United States)

    Weber, Waldemar; Andersson, Jan T


    The separation properties of six novel stationary phases for gas chromatography, commercially available from Sigma-Aldrich (Supelco) and based on ionic liquids (ILs), were investigated. The linear solvation energy relationship model (LSER) was used to describe the molecular interactions between these stationary phases and 30 solutes. The solutes belong to different groups of compounds, like haloalkanes, alcohols, ketones, aromatics, aliphatics, and others. A good description of different interactions, as described by the LSER model, could be achieved. The calculated values of system constants for the ionic liquid phases were compared with constants of commonly used standard phases like a 5 % phenyl/95 % dimethyl siloxane and a polyethylene glycol phase. The solute descriptors are in good agreement with those found by previous authors who have used the LSER model for 44 different ionic liquids as stationary phase. The experiments were carried out at two temperatures to evaluate the influence on the phase parameters and separation characteristics. The interactions of different functional groups with the IL phases are discussed. These novel IL phases are a promising replacement of or an addition to common polar phases. Based on the evaluated phase properties, several possibilities for applications of these novel phases are shown.

  14. Theoretical investigation of one-photon and two-photon absorption properties for multiply N-confused porphyrins. (United States)

    Yang, Zhao-Di; Feng, Ji-Kang; Ren, Ai-Min; Sun, Chia-Chung


    We have theoretically investigated a series of multiply N-confused porphyrins and their Zn or Cu complexes for the first time by using DFT(B3LYP/6-31G*) and ZINDO/SOS methods. The electronic structure, one-photon absorption (OPA), and two-photon absorption (TPA) properties have been studied in detail. The calculated results indicate that the OPA spectra of multiply N-confused porphyrins are red-shifted and the OPA intensities decrease compared to normal porphyrin. The maximum two photon absorption wavelengths lambda(max) are blue-shifted and the TPA cross sections delta(max) are increased 22.7-112.1 GM when the N atoms one by one are inverted from core to beta position to form multiply N-confused porphyrins. Especially delta(max) of N3CP get to 164.7 GM. The electron donors -C6F5s at meso-position can make the TPA cross section delta(max) increase. After forming metal complexes with Cu or Zn, the TPA properties of multiply N-confused porphyrins are further increased except for N3CP, N4CP. Our theoretical findings demonstrate that the multiply N-confused prophyrins as well as their metal complexes and derivatives are promising molecules that can be assembled series of materials with large TPA cross section, and are sure to be the subject of further investigation.

  15. Origin of electronic properties of PbGa{sub 2}Se{sub 4} crystal: Experimental and theoretical investigations

    Energy Technology Data Exchange (ETDEWEB)

    Babuka, T. [Institute of Physics, Jan Dlugosz University in Czestochowa, Al. Armii Krajowej 13/15, 42-200 Czestochowa (Poland); Kityk, I.V. [Faculty of Electrical Engineering, Czestochowa University Technology, Al. Armii Krajowej 17, 42-201 Czestochowa (Poland); Department of Solid State Physics, Eastern European National University, Voli 13 Ave., Lutsk 43205 (Ukraine); Parasyuk, O.V. [Department of Inorganic and Physical Chemistry, Eastern European National University, Voli 13 Ave., Lutsk 43205 (Ukraine); Myronchuk, G. [Department of Solid State Physics, Eastern European National University, Voli 13 Ave., Lutsk 43205 (Ukraine); Khyzhun, O.Y. [Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky Street, Kyiv 03142 (Ukraine); Fedorchuk, A.O. [Lviv National University of Veterinary Medicine and Biotechnologies, Department of Inorganic and Organic Chemistry, Pekarska St. 50, 79010 Lviv (Ukraine); Makowska-Janusik, M., E-mail: [Institute of Physics, Jan Dlugosz University in Czestochowa, Al. Armii Krajowej 13/15, 42-200 Czestochowa (Poland)


    Graphical abstract: In the presented work the structural and electronic properties of the PbGa{sub 2}Se{sub 4} single crystal were investigated experimentally as well as theoretically. The XPS spectra, Urbach’s rule and steepness parameters of PbGa{sub 2}Se{sub 4} single crystal have been investigated for the first time. The quantum chemical calculations were also never performed before for the studied structure. The theoretically obtained data help to explain the properties of material. - Highlights: • Urbach’s rule and steepness parameters for PbGa{sub 2}Se{sub 4} crystals explored for the first time. • Non-reactivity of the PbGa{sub 2}Se{sub 4} surface was established by XPS. • DFT approach shows its efficiency to describe electronic properties of PbGa{sub 2}Se{sub 4}. • Electronic parameters are affected by existence of electron–phonon interaction. - Abstract: The PbGa{sub 2}Se{sub 4} crystal is a promising material for optoelectronic applications. It is caused by coexistence of the large polarized Pb cations and a huge contribution of anharmonic phonon subsystem caused by chalcogenide anions. In the present work the electronic and optical properties of the mentioned material were studied theoretically as well as experimentally by optical and X-ray photoelectron spectroscopy methods. The DFT approach has been used for the quantum chemical electronic properties calculations. Urbach rule and steepness parameters of the PbGa{sub 2}Se{sub 4} crystal have been evaluated for the first time. These parameters and Urbach energies increase with increasing temperature of the samples that is typical for the semiconducting materials. The XPS measurements of the investigated crystal reveal that all the spectral features are originated from core-level states of the constituent elements. Simultaneously these results also confirm non-reactivity of the PbGa{sub 2}Se{sub 4} surface. However, the titled single crystal possesses a number of intrinsic structural

  16. A theoretical investigation on the parametric instability excited by X-mode polarized electromagnetic wave at Tromsø (United States)

    Wang, Xiang; Cannon, Patrick; Zhou, Chen; Honary, Farideh; Ni, Binbin; Zhao, Zhengyu


    Recent ionospheric modification experiments performed at Tromsø, Norway, have indicated that X-mode pump wave is capable of stimulating high-frequency enhanced plasma lines, which manifests the excitation of parametric instability. This paper investigates theoretically how the observation can be explained by the excitation of parametric instability driven by X-mode pump wave. The threshold of the parametric instability has been calculated for several recent experimental observations at Tromsø, illustrating that our derived equations for the excitation of parametric instability for X-mode heating can explain the experimental observations. According to our theoretical calculation, a minimum fraction of pump wave electric field needs to be directed along the geomagnetic field direction in order for the parametric instability threshold to be met. A full-wave finite difference time domain simulation has been performed to demonstrate that a small parallel component of pump wave electric field can be achieved during X-mode heating in the presence of inhomogeneous plasma.

  17. Theoretical investigations of α,α,α-trifluoro-3, -p and o-nitrotoluene by means of density functional theory. (United States)

    Yildirim, G; Senol, S D; Dogruer, M; Ozturk, O; Senol, A; Tasci, A T; Terzioglu, C


    This study reports the optimized molecular structures, vibrational frequencies including Infrared intensities and Raman activities, corresponding vibrational assignments, (1)H and (13)C NMR chemical shifts, the magnitudes of the JCH and JCC coupling constants, Ultraviolet-visible (UV-vis) spectra, thermodynamic properties and atomic charges of the title compounds, α,α,α-trifluoro-3, -p and o-nitrotoluene, in the ground state by means of the density functional theory (DFT) with the standard B3LYP/6-311++G(d,p) method and basis set combination for the first time. Theoretical vibrational spectra were interpreted by normal coordinate analysis based on scaled density functional force field. The results show that the vibrational frequencies and chemical shifts calculated were obtained to be in good agreement with the experimental data. Based on the comparison between experimental results and theoretical data, the calculation level chosen is powerful approach for understanding the identification of all the molecules studied. In addition, not only were frontier molecular orbitals (HOMO and LUMO), molecular electrostatic potential (MEP) and electrostatic potential (ESP) simulated but also the dipole moment, softness, electronegativity, chemical hardness, electrophilicity index, transition state and energy band gap values were predicted. According to the investigations, all compounds were found to be useful to bond metallically and interact intermolecularly; however, the thermodynamic properties confirm that the α,α,α-trifluoro-p-nitrotoluene was more reactive and more polar than the others.

  18. Theoretical and experimental investigations of electron emission in C{sup 6+} + H{sub 2}O collisions

    Energy Technology Data Exchange (ETDEWEB)

    Dal Cappello, C. [Universite Paul Verlaine-Metz, Laboratoire de Physique Moleculaire et des Collisions (LPMC), Institut Jean Barriol (FR2843), Institut de Physique de Metz, 1 Boulevard Arago, 57078 Metz Cedex 3 (France); Champion, C. [Universite Paul Verlaine-Metz, Laboratoire de Physique Moleculaire et des Collisions (LPMC), Institut Jean Barriol (FR2843), Institut de Physique de Metz, 1 Boulevard Arago, 57078 Metz Cedex 3 (France)], E-mail:; Boudrioua, O.; Lekadir, H. [Universite Paul Verlaine-Metz, Laboratoire de Physique Moleculaire et des Collisions (LPMC), Institut Jean Barriol (FR2843), Institut de Physique de Metz, 1 Boulevard Arago, 57078 Metz Cedex 3 (France); Sato, Y. [Gunma University, Research Center for Heavy-Ion Medicine, Gunma (Japan); Ohsawa, D. [Kyoto University, Radioisotope Research Center, Kyoto (Japan)


    Theoretical differential and total cross sections for the direct ionization process of water vapour by 6 MeV/u C{sup 6+} ions are compared to new experimental measurements performed by the dedicated apparatus already used for measuring the energy and angular distributions of secondary electrons emitted from water vapour by fast heavy-ion impact [D. Ohsawa, H. Kawauchi, M. Hirabayashi, Y. Okada, T. Homma, A. Higashi, S. Amano, Y. Hashimoto, F. Soga, Y. Sato, Nucl. Instr. and Meth. B 227 (2005) 431]. In the present work, ab initio calculations have been carried out in the first Born approximation by using an accurate molecular wave function for describing the initial bound state of the target. The calculated cross sections exhibit good agreement with the present experimental measurements and compare relatively well to the existing semi-empirical results over the entire angular and energy ranges investigated here. Free from any adjustable parameter, the proposed theoretical approach describes in detail the complete kinematics of the water molecule ionization process by highly energetic carbon ions, and could therefore be easily used for modelling the heavy charged-particle transport in the biological matter.

  19. Theoretical and experimental investigations of quasi-continuous wave diode arrays side-pumped Yb:YAG slab laser

    Institute of Scientific and Technical Information of China (English)

    Wu Hai-Sheng; Yan Ping; Gong Ma-Li; Liu Qiang


    An analytical model of quasi-continuous wave (quasi-CW) diode array side-pumped slab laser for Yb:YAG oscillator in long-pulse free-running has been developed based on the CW model. In this model we first introduce a new parameter,pump pulse width, and make the model available for use in the quasi-CW model. We also give an analytical equation of laser delay time to calculate the laser pulse width. A detailed model is also presented for a new structure laser design, taking account of the geometry of Yb:YAG slab. A quasi-CW diode array side-pumped Yb:YAG slab laser is investigated theoretically and experimentally. Experiments yield a quasi-CW output energy up to 20.36 mJ with the laser pulse width of 654.55μs at 1049 nm when the diode arrays operate at 25 Hz and 1 ms pulse width. The crystal dimensions are 3 mm×8 mm× 1 mm and the doping density is 10 at.%. The experimental results are in good agreement with the predictions of the theoretical model.

  20. Theoretical investigation on the steady-state natural circulation characteristics of a new type of pressurized water reactor

    Institute of Scientific and Technical Information of China (English)


    This article presents a theoretical investigation on the steady-state natural circulation characteristics of a new type of pressurized water reactor. Through numerically solving the one-dimensional steady-state single-phase conservative equations for the primary circuit and the steady-state two-phase drift-flux conservative equations for the secondary side of the steam generator, the natural circulation characteristics were studied. On the basis of the preliminary calculation analysis, it was found that natural circulation mass flow rate was proportional to the exponential function of the power and that the value of the exponent is related to the operating conditions of the secondary side of the steam generator. The higher the outlet pressure of the secondary side of the steam generator, the higher the primary natural circulation mass flow rate. The larger height difference between the core center and the steam generator center is favorable for the heat removal capacity of the natural circulation.

  1. Theoretical investigation on the effect of ASE noise for amplified fiber loop ring-down gas sensing (United States)

    Cheng, Chunfu; Zeng, Yan; Ou, Yiwen; Zhang, Jinye; Lv, Qinghua; Zhu, Jinrong; Lv, Hui


    The effect of spontaneous emission (ASE) noise produced by the erbium-doped fiber amplifier (EDFA) on the performance of amplified fiber loop ring-down gas sensing systems is theoretically investigated. The results show that the EDFA placed after the gas cell with a smaller ASE noise can improve the measurement accuracy. The more narrower the noise equivalent optical bandwidth of the optical band pass filter following the EDFA is, the up shift of baseline of ring-down signal can be more effectively suppressed and thus improving the measurement accuracy. It is also found the longer ring-down time can be obtained by reducing the input power due to the smaller gain fluctuations of the EDFA.

  2. Theoretical investigation on crystal structure, detonation performance and thermal stability of a high density cage hexanitrohexaazaisowurtzitane derivative

    Indian Academy of Sciences (India)

    Li Xiao-Hong; Cui Hong-Ling; Li Li-Ben; Zhang Xian-Zhou


    Density functional theory calculations were performed to study the new polynitro cage compound with the similar framework of HNIW. IR spectrum, heat of formation and thermodynamic properties were predicted. The bond dissociation energies and bond orders for the weakest bonds were analysed to investigate the thermal stability of the title compound. The detonation and pressure were evaluated by using the Kamlet-Jacobs equations based on the theoretical density and condensed HOFs. In addition, the results show that there exists an essentially linear relationship between the WBIs of N-NO2 bonds and the charges -QNO2 on the nitro groups. The crystal structure obtained by molecular mechanics belongs to P21/C space group, with lattice parameters Z = 4, a = 12.3421 Å, b = 24.6849 Å, c = 20.4912 Å, = 1.896 g cm-3. The designed compound has high thermal stability and good detonation properties and is a promising high energy density compound.

  3. A Theoretical investigation on HC Mixtures as Possible Alternatives to R134a in Vapor Compression Refrigeration

    Directory of Open Access Journals (Sweden)

    Feiza Memet


    Full Text Available This paper provides a theoretical comparison of the performance of refrigerants in use in a vapor comparison cycle. It is about the phase-out of R134a from actual refrigeration system, comparison being performed for this chemical and two more ecological mixtures: R290/R600a described as (30/70 and (40/60. Were investigated effects of condensation temperatures and evaporation temperatures on performance measures as COP (Coefficient of Performance and VCC (volumetric cooling capacity. COP is a measure of the performance of the refrigeration cycle, while VCC is an indicator of compressor size. Results of this study will reveal that R290/R600a (30/70 is a good option when it is about substitution of R134a, from energy efficiency point of view, in terms of COP. R290/R600a (40/60 has VCC values bellow the ones of R134a, but comparable.

  4. Experimental and theoretical investigations of electronic and atomic structure of Si-nanocrystals formed in sapphire by ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Wainstein, D; Kovalev, A; Tetelbaum, D; Mikhailov, A [Surface Phenomena Researches Group, 2-nd Baumanskaya str. 9/23, CNIICHERMET, office 475, Moscow, 105005 (Russian Federation); Bulutay, C; Aydinli, A [Department of Physics and National Nanotechnology Research Center, Bilkent University, Ankara, 06800 Turkey (Turkey)], E-mail:


    The semiconductor nanocomposites based on Si nanocrystals in dielectric matrices attract a great amount of attention due to their ability for luminescence in visible and near-IR part of the electromagnetic spectrum. Si nanocrystals in sapphire matrix were formed by Si{sup +} ion implantation with doses from 5x10{sup 16} to 3x10{sup 17} cm{sup -2} at an accelerating voltage 100 kV and post-implantation annealing at 500 - 1100 {sup 0}C for 2 hours. Depth distribution of lattice defects, impurities and Si nanocrystals, the peculiarities of interband electronic transitions were investigated by XPS and HREELS. The molecular orbitals and local electronic structure of the Al{sub 2}O{sub 3} matrix with Si nanocrystals was calculated using an atomistic pseudopotential technique. The electronic structure of Si nanocrystals as determined from HREELS measurements is in good agreement with the theoretically calculated electronic structure for Si nanocrystals.

  5. Experimental and theoretical investigations of electronic and atomic structure of Si-nanocrystals formed in sapphire by ion implantation (United States)

    Wainstein, D.; Kovalev, A.; Tetelbaum, D.; Mikhailov, A.; Bulutay, C.; Aydinli, A.


    The semiconductor nanocomposites based on Si nanocrystals in dielectric matrices attract a great amount of attention due to their ability for luminescence in visible and near-IR part of the electromagnetic spectrum. Si nanocrystals in sapphire matrix were formed by Si+ ion implantation with doses from 5×1016 to 3×1017 cm-2 at an accelerating voltage 100 kV and post-implantation annealing at 500 - 1100 °C for 2 hours. Depth distribution of lattice defects, impurities and Si nanocrystals, the peculiarities of interband electronic transitions were investigated by XPS and HREELS. The molecular orbitals and local electronic structure of the Al2O3 matrix with Si nanocrystals was calculated using an atomistic pseudopotential technique. The electronic structure of Si nanocrystals as determined from HREELS measurements is in good agreement with the theoretically calculated electronic structure for Si nanocrystals.

  6. Theoretical Investigation of Peak-Delay Force Reduction for Caissons Exposed to Non-breaking Short-Crested Waves

    DEFF Research Database (Denmark)

    Burcharth, H. F.; Liu, Z.

    In nature coastal structures are exposed to oblique short-crested waves. The effect of wave incident angle on total wave force on a long caisson are twofold. The one is the force reduction due to the reduction of instantaneous point pressure on the caisson, named point-pressure force reduction...... on the peak-delay force reduction of caissons exposed to non-breaking short-crested waves. Battjes (1982) has investigated theoretically the peak-delay force reduction of shortcrested waves with only one frequency component. Such a force reduction factor cannot be applied because in nature waves are composed...... of many linear components with various frequencies. In this paper the peak-delay force reduction factor is defined on basis of zero-moment of the force spectrum. Based on linear wave theory, formulae for calculation of peakdelay force reduction factor for linear, long-crested and short-crested non-breaking...

  7. Martensitic transformation in Heusler alloys Mn{sub 2}YIn (Y=Ni, Pd and Pt): Theoretical and experimental investigation

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Hongzhi, E-mail: [School of Material Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Liu, Bohua; Xin, Yuepeng; Jia, Pengzhong; Meng, Fanbin [School of Material Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Liu, Enke; Wang, Wenhong; Wu, Guangheng [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China)


    The martensitic transformation and electronic structure of Heusler alloys Mn{sub 2}YIn (Y=Ni, Pd, Pt) have been investigated by both first-principles calculation and experimental investigation. Theoretical calculation reveals that, the energy difference ΔE between the tetragonal martensitic phase and cubic austenitic phase increases with Y varying from Ni to Pt in Mn{sub 2}YIn. Thus a structural transition from cubic to tetragonal is most likely to happen in Heusler alloy Mn{sub 2}PtIn. A single Heusler phase can be obtained in both Mn{sub 2}PtIn and Mn{sub 2}PdIn. A martensitic transformation temperature of 615 K has been identified in Mn{sub 2}PtIn. And in Mn{sub 2}PdIn, the austenitic phase is stable and no martensitic transformation is observed till 5 K. This indicates there may exist a positive relation between ΔE and martensitic transformation temperature. Calculated results show that Mn{sub 2}YIn are all ferrimagnets in both austenitic and martensitic phases. The magnetic properties are mainly determined by the antiparallel aligned Mn spin moments. These findings can help to develop new FSMAs with novel properties. - Highlights: • Positive relation between ΔE and martensitic transformation temperature has been observed. • Heusler alloy Mn{sub 2}PdIn has been synthesized successfully and investigated. • Martensitic transformation in Heusler alloys can be predicted by first -principles calculations.

  8. Theoretical Investigation of the Structural, Elastic, and Thermodynamic Properties of MgAl2O4 Spinel under High Pressure (United States)

    Mao, Xiao-Chun; Liu, Ke; Hou, Bao-Sen; Tan, Jiao; Zhou, Xiao-Lin


    The structural and elastic properties of MgAl2O4 spinel under high pressure are investigated through the first-principles calculations. The lattice parameters and elastic constants are in good agreement with the available experimental and theoretical results. The polycrystalline elastic moduli of MgAl2O4 spinel are calculated using the Voigt-Reuss-Hill approximation. By the elastic stability criteria, the MgAl2O4 spinel is mechanically stable within 80 GPa. MgAl2O4 possesses ductile nature, and the ductility is enhanced with the increase of pressure. The sound velocities over a wide range of pressures are also obtained. Furthermore, the elastic anisotropies of MgAl2O4 are investigated via the various anisotropic indexes and the 3D surface constructions. It is found that MgAl2O4 is isotropic for bulk modulus, while is anisotropic for shear modulus and Young's modulus, and the elastic anisotropy of MgAl2O4 increases due to the applying pressure. Besides, the directions with smaller values of shear modulus for MgAl2O4 will deform preferentially under high hydrostatic pressure. Through the quasi-harmonic Debye model, we also investigated the thermodynamic properties of MgAl2O4 spinel.

  9. Applying Chromatography. (United States)

    Klein, Jessie W.; Patev, Paul


    Presents three experiments to introduce students to different kinds of chromatography: (1) paper chromatography; (2) gel filtration chromatography; and (3) reverse-phase liquid chromatography. Written in the form of a laboratory manual, explanations of each of the techniques, materials needed, procedures, and a glossary are included. (PVD)

  10. New gas chromatography-olfactometric investigative method, and its application to cooked Silurus glanis (European catfish) odor characterization. (United States)

    Hallier, Arnaud; Courcoux, Philippe; Sérot, Thierry; Prost, Carole


    A new gas chromatography-olfactometric method, gas chromatography-global olfactometry omission detection (GC-GOOD), was applied to dynamic headspace odor extracts of Silurus glanis (European catfish). The GC-GOOD method is based on the omission test theory and uses a gas chromatograph coupled with a three-way valve and an a flame ionization detector. The GC-GOOD method enabled the identification of key families of volatile compounds in the S. glanis global odor and the elucidation of the interactions occurring between these families. Significant main effects were observed for the families of volatile compounds exhibiting cooked odor, grassy odor and alcohol, solvent and plastic odors. Omission of these families involved a loss of odor similarity.

  11. Theoretical investigation of two model systems for molecular photoswitch functionality. I. 2-(4-nitropyrimidin-2-yl)ethenol (United States)

    Woywod, Clemens; Csehi, András; Halász, Gábor J.; Ruud, Kenneth; Vibók, Ágnes


    The ground and five lowest-lying electronically excited singlet states of 2-(4-nitropyrimidin-2-yl)ethenol (NPE) have been studied theoretically using the complete active space self-consistent-field (CASSCF), Møller-Plesset second-order perturbation theory (MP2) and second-order multi-configurational perturbation theory (CASPT2) methods. The molecule can be regarded as being composed of a frame and a crane component and is characterised by the existence of two planar minima of similar energy on the ground-state potential energy (PE) surface. This work explores the possibility of an excited-state intramolecular hydrogen transfer (ESIHT) process in NPE. A hypothetical reaction coordinate has been constructed for NPE. State-averaged CASSCF and CASPT2 calculations of the six lowest-lying singlet states have been performed for the isomerisation. Adiabatic and simplified quasi-diabatic PE and transition dipole moment functions have been constructed. The computations indicate that there exist substantial barriers for the rotation process on the adiabatic PE surfaces of all the five excited states investigated. The six quasi-diabatic electronic states considered here decompose into two classes based on whether the electronic wave functions depend weakly or strongly on the nuclear displacement, subject to the effect of the torsion on relevant molecular orbitals.

  12. Theoretical investigations on SiC2 siligraphene as promising metal-free catalyst for oxygen reduction reaction (United States)

    Dong, Huilong; Lin, Bin; Gilmore, Keith; Hou, Tingjun; Lee, Shuit-Tong; Li, Youyong


    The design and discovery of high-performance metal-free catalytic materials for oxygen reduction reaction (ORR) electrocatalysis is vital for the development of fuel cells. By performing density functional theory (DFT) calculations, we investigate the potential applications of SiC2 siligraphene (g-SiC2) as metal-free ORR catalyst. The g-SiC2 exhibits higher adsorption affinity for the O2 molecule and other ORR intermediates than the traditional Pt (111), and shows good tolerance against CO poisoning. The detailed LH and ER mechanisms in catalyzing ORR by g-SiC2 are simulated and discussed, both in acidic and alkaline environment. We find that, in alkaline environment, the g-SiC2 presents a very low activation barrier (0.16 eV) for the rate determining step (RDS) and shows no overpotential at the equilibrium potential. Our theoretical simulations validate that the siligraphene with alternatively arranged Si and C atoms holds great potential as ORR catalyst in alkaline environment.

  13. Electrochemical and theoretical investigation on the corrosion inhibition of mild steel by thiosalicylaldehyde derivatives in hydrochloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Behpour, M. [Department of Chemistry, Faculty of Science, University of Kashan, Kashan (Iran, Islamic Republic of)], E-mail:; Ghoreishi, S.M.; Soltani, N.; Salavati-Niasari, M.; Hamadanian, M.; Gandomi, A. [Department of Chemistry, Faculty of Science, University of Kashan, Kashan (Iran, Islamic Republic of)


    Inhibitory effect of three Schiff bases 2-{l_brace}[(2-sulfanylphenyl)imino]methyl{r_brace}]phenol (A), 2-{l_brace}[(2)-1-(4-methylphenyl)methylidene]amino{r_brace}-1-benznethiol (B), and 2-[(2-sulfanylphen-yl)ethanimidoyl)]phenol (C) on corrosion of mild steel in 15% HCl solution has been studied using weight loss measurements, polarization and electrochemical impedance spectroscopy (EIS) methods. The results of the investigation show that the compounds A and B with mean efficiency of 99% at 200 mg/L additive concentration have fairly good inhibiting properties for mild steel corrosion in hydrochloric acid, and they are as mixed inhibitor. All measurements show that inhibition efficiencies increase with increase in inhibitor concentration. This reveals that inhibitive actions of inhibitors were mainly due to adsorption on mild steel surface. Adsorption of these inhibitors follows the Langmuir adsorption isotherm. Thermodynamic adsorption parameters (K{sub ads}, {delta}G{sub ads}) of studied Schiff bases were calculated using the Langmuir adsorption isotherm. Activation parameters of the corrosion process such as activation energies, E{sub a}, activation enthalpies, {delta}H{sup *}, and activation entropies, {delta}S{sup *}, were calculated by the obtained corrosion currents at different temperatures. Obvious correlation was found between the corrosion inhibition efficiency and the calculated parameters. The obtained theoretical results have been adapted with the experimental data.

  14. Theoretical and experimental investigations on corrosion control of 65Cu–35Zn brass in nitric acid by two thiophenol derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Ebrahimzadeh, M.; Gholami, M.; Momeni, M. [Metallurgical and Materials Engineering Department, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad 91775-1111 (Iran, Islamic Republic of); Kosari, A., E-mail: [Metallurgical and Materials Engineering Department, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad 91775-1111 (Iran, Islamic Republic of); Moayed, M.H. [Metallurgical and Materials Engineering Department, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad 91775-1111 (Iran, Islamic Republic of); Davoodi, A. [Materials Engineering Department, Hakim Sabzevari University, Sabzevar 391 (Iran, Islamic Republic of)


    Highlights: • Two organic compounds were studied as corrosion inhibitor for brass. • Three equivalent circuits were used to fit the impedance spectra. • Langmuir isotherm was used to determine the inhibitor adsorption type. • An increase in corrosion resistance of brass in the range of 20–35 was detected. • Correlation between quantum chemical and experimental efficiencies was acquired. - Abstract: Inhibitive performance of two thiophenol derivatives namely 4-aminothiophenol (4-ATP) and 4-amino phenol disulfide (4-APD) on corrosion behavior of 65Cu–35Zn brass in 0.5 M HNO{sub 3} was investigated. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) and also quantum chemical study were used. 4-APD showed higher efficiency at low temperatures while for higher temperatures the 4-ATP is more efficient. The inhibitors obey Langmuir isotherm and its adsorption is both chemical and physical type. Quantum chemical study reveals that the benzene ring, S and N atoms can be suitable sites for adsorption onto surface. Finally, an acceptable correlation between the theoretical and experimental inhibitor efficiency was acquired.

  15. Theoretical investigation of the competitive mechanism between dissociation and ionization of H₂⁺ in intense field. (United States)

    Yao, Hongbin; Zhao, Guangjiu


    The competitive mechanism between dissociation and ionization of hydrogen molecular ion in intense field has been theoretically investigated by using an accurate non-Born-Oppenheimer method. The relative yield of fragments indicates that the dissociation and ionization channels are competitive with the increasing laser intensity from 5.0 × 10(13) to 2.0 × 10(14) W/cm(2). In the case of intensity lower than 1.0 × 10(14) W/cm(2), the dissociation channel is dominant, with a minor contribution from ionization. The mechanism of dissociation includes the contributions from the bond softening, bond hardening, below-threshold dissociation, and above-threshold dissociation, which are strongly dependent on the laser intensity and initial vibrational state. Furthermore, the ionization dominates over the dissociation channel at the highest intensity of 2.0 × 10(14) W/cm(2). The reasonable origin of ionization is ascribed as the above-threshold Coulomb explosion, which has been demonstrated by the space-time dependent ionization rate. Moreover, the competition mechanism between dissociation and ionization channels are displayed on the total kinetic energy resolved (KER) spectra, which could be tested at current experimental conditions.

  16. Investigating Brain Network Characteristics Interrupted by Covert White Matter Injury in Patients with Moyamoya Disease: Insights from Graph Theoretical Analysis. (United States)

    Kazumata, Ken; Tha, Khin Khin; Narita, Hisashi; Shichinohe, Hideo; Ito, Masaki; Uchino, Haruto; Abumiya, Takeo


    Chronic ischemia in adult moyamoya disease (MMD) reduces the integrity of normal-appearing white matter (WM). We investigated whether covert WM impairment alters large-scale brain networks and specific neural circuits associated with neurocognitive dysfunction in MMD. Forty-six participants (control, n = 23; MMD, n = 23) were examined using diffusion tensor imaging and streamline tractography. Structural connectivity among 90 cortical and subcortical brain regions was evaluated using the mean fractional anisotropy along the fiber tracts. Graph theoretical analysis was used to measure network parameters and inter-regional connectivity. Global network parameters were reduced in patients with MMD, including cluster coefficient (controls vs. MMD: 3.62 ± 0.24 vs. 3.26 ± 0.36; P < 0.0001), characteristic path length (controls vs. MMD: 1.20 ± 0.02 vs. 1.17 ± 0.01; P < 0.001), and small-world property (controls vs. MMD: 3.07 ± 0.18 vs. 2.83 ± 0.27; P < 0.001). Reduced pairwise connectivity was found in prefrontal neural circuits within the middle/inferior frontal gyrus; supplementary motor area; and insular, inferior temporal, and dorsal cingulate cortices. Covert WM microstructural changes in patients with MMD alter large-scale brain networks, as well as lateral prefrontal neural circuits. Evaluation of structural connectivity may be useful to assess the severity of chronic ischemic injury from a network perspective.

  17. Theoretical investigation of silicide Schottky barrier detector integrated in horizontal metal-insulator-silicon-insulator-metal nanoplasmonic slot waveguide. (United States)

    Zhu, Shiyang; Lo, G Q; Kwong, D L


    An ultracompact integrated silicide Schottky barrier detector (SBD) is designed and theoretically investigated to electrically detect the surface plasmon polariton (SPP) propagating along horizontal metal-insulator-silicon-insulator-metal nanoplasmonic slot waveguides at the telecommunication wavelength of 1550 nm. An ultrathin silicide layer inserted between the silicon core and the insulator, which can be fabricated precisely using the well-developed self-aligned silicide process, absorbs the SPP power effectively if a suitable silicide is chosen. Moreover, the Schottky barrier height in the silicide-silicon-silicide configuration can be tuned substantially by the external voltage through the Schottky effect owing to the very narrow silicon core. For a TaSi(2) detector with optimized dimensions, numerical simulation predicts responsivity of ~0.07 A/W, speed of ~60 GHz, dark current of ~66 nA at room temperature, and minimum detectable power of ~-29 dBm. The design also suggests that the device's size can be reduced and the overall performances will be further improved if a silicide with smaller permittivity is used.

  18. Tautomerism in o-hydroxyanilino-1,4-naphthoquinone derivatives: Structure, NMR, HPLC and density functional theoretic investigations (United States)

    Bhand, Sujit; Patil, Rishikesh; Shinde, Yogesh; Lande, Dipali N.; Rao, Soniya S.; Kathawate, Laxmi; Gejji, Shridhar P.; Weyhermüller, Thomas; Salunke-Gawali, Sunita


    Structure and spectral characteristics of 'Ortho' ((E)-4-hydroxy-2-(2‧-(4‧-R)-hydroxyphenyl)-imino)-naphthalen-1(2H)-one) and 'para' (2-(2‧-(4‧-R)-hydroxyphenyl)-amino)-1,4-naphthoquinone) tautomers of o-hydroxyanilino-1,4-naphthoquinone derivatives (Rdbnd H, 1A; sbnd CH3, 2A; and -Cl, 3A) are investigated using the 1H, 13C, DEPT, gDQCOSY, gHSQCAD NMR, HPLC, cyclic voltammetry techniques combined with the density functional theory. The compound 2A crystallizes in monoclinic space group P21/c. wherein the polymer chain is facilitated via Osbnd H⋯O and Csbnd H⋯O intermolecular hydrogen bonding. Marginal variations in bond distances in quinonoid and aminophenol moieties render structural flexibility to these compounds those in solution exist as exist in 'ortho - para' tautomers. 1H and 13C NMR spectra in DMSO-d6 showed two sets of peaks in all compounds; whereas only the para tautomer of for 1A and 2A, the para tautomer is predominant in CD3CN solution. Further the ortho-para interconversion is accompanied by a large up-field signals for C(3)sbnd H(3) in their 1H and 13C NMR spectra. These inferences are corroborated by the density functional theoretic calculations.

  19. Theoretical investigation of fabrication-related disorders on the properties of subwavelength metal-dielectric-metal plasmonic waveguides. (United States)

    Min, Changjun; Veronis, Georgios


    We theoretically investigate the effect of fabrication-related disorders on subwavelength metal-dielectric-metal plasmonic waveguides. We use a Monte Carlo method to calculate the roughness-induced excess attenuation coefficient with respect to a smooth waveguide. For small roughness height, the excess optical power loss due to disorder is small compared to the material loss in a smooth waveguide. However, for large roughness height, the excess attenuation increases rapidly with height and the propagation length of the optical mode is severely affected. We find that the excess attenuation is mainly due to reflection from the rough surfaces. However, for small roughness correlation lengths, enhanced absorption is the dominant loss mechanism due to disorder. We also find that the disorder attenuation due to reflection is approximately maximized when the power spectral density of the disordered surfaces at the Bragg spatial frequency is maximized. Finally, we show that increasing the modal confinement or decreasing the guide wavelength, increase the attenuation due to disorder.

  20. Adaptive angular-velocity Vold-Kalman filter order tracking - Theoretical basis, numerical implementation and parameter investigation (United States)

    Pan, M.-Ch.; Chu, W.-Ch.; Le, Duc-Do


    The paper presents an alternative Vold-Kalman filter order tracking (VKF_OT) method, i.e. adaptive angular-velocity VKF_OT technique, to extract and characterize order components in an adaptive manner for the condition monitoring and fault diagnosis of rotary machinery. The order/spectral waveforms to be tracked can be recursively solved by using Kalman filter based on the one-step state prediction. The paper comprises theoretical derivation of computation scheme, numerical implementation, and parameter investigation. Comparisons of the adaptive VKF_OT scheme with two other ones are performed through processing synthetic signals of designated order components. Processing parameters such as the weighting factor and the correlation matrix of process noise, and data conditions like the sampling frequency, which influence tracking behavior, are explored. The merits such as adaptive processing nature and computation efficiency brought by the proposed scheme are addressed although the computation was performed in off-line conditions. The proposed scheme can simultaneously extract multiple spectral components, and effectively decouple close and crossing orders associated with multi-axial reference rotating speeds.

  1. Design and theoretical investigation of a silicon-on-insulator based electro-optical logic gate device (United States)

    Li, Lei; Qi, Zhipeng; Hu, Guohua; Yun, Binfeng; Zhong, Yuan; Cui, Yiping


    A compact electro-optical "NOR" logic gate device based on silicon-on-insulator (SOI) platform is proposed and investigated theoretically. By introducing a hook-type waveguide, the signal could be coupled between the bus and hook-type waveguide to form an optical circuit and realize NOR logic gate. We can easily realize the NOR logical function by the voltage applied on the coupling components. The numerical simulation shows that a high coupling efficiency of more than 99% is obtained at the wavelength of 1550 nm, and the footprint of our device is smaller than 90 μm2. In addition, the response time of the proposed NOR logic gate is 3 ns with a switching voltage of 1.8 V. Moreover, it is demonstrated that such NOR logic gate device could obtain an extinction ratio of 21.8 dB. Thus, it has great potential to achieve high speed response, low power consumption, and small footprint, which fulfill the demands of next-generation on-chip computer multiplex processors.

  2. Porphyrin dyes on TiO2 surfaces with different orientations: a photophysical, photovoltaic, and theoretical investigation. (United States)

    Si, Liping; He, Hongshan


    Porphyrin dyes with a triphenylamino group as an electron donor, para- or meta-benzoic acids as electron acceptors, and hydrogen (H) or mesityl (M) substituents on the meso position as auxiliary groups were synthesized. Their photophysical properties and photovoltaic performance in dye-sensitized solar cells were investigated. All four porphyrins exhibited similar photophysical properties in the solution and dye-loading densities on the surface of TiO2 nanoparticles; however, the p-benzoic acid functionalized porphyrins, p-H(M)PZn, gave better photovoltaic performance than m-benzoic acid functionalized porphyrins, m-H(M)PZn. Theoretical calculations indicated that the electron density on the frontier molecular orbital was more delocalized to p-benzoic acid than to m-benzoic acid. Absorption spectra indicated the stronger H-aggregation in m-H(M)PZn than that in p-H(M)PZn on the surface of TiO2 nanoparticles. The mesityl groups in the meso positions reduced the dye-loading density due to steric hindrance between dyes. As a result, the p-MPZn exhibited the best energy conversion efficiency among the four porphyrins studied. This efficiency was further enhanced when a complementary dye BET was used.

  3. Theoretical and Experimental Investigation of Gas Flows, Powder Transport and Heating in Coaxial Laser Direct Metal Deposition (DMD) Process (United States)

    Kovalev, O. B.; Zaitsev, A. V.; Novichenko, D.; Smurov, I.


    The results of theoretical and experimental investigations of direct metal deposition (DMD) processes involving a CO2-laser with the power up to 5 kW and wave length of 10.6 μm are presented. The physical and mathematical model of multi-layer gas flows with gas-jet transportation of metal powder particles has been developed. To simulate the flows of carrier and shaping gases in annular channels of a triple coaxial nozzle, Navier-Stokes equations were applied for an axisymmetric flow. Thermodynamics and powder particles transport are calculated from a discrete-trajectory model with due regard to particle collision with solid walls of the transport nozzle. It is shown that particles may overheat on their way between the nozzle and substrate; the overheating depends on the trajectories by which particles move, on their size, and time of their retention in the laser-radiation region. The results of performed experimental researches on DMD processes visualization are presented. Some results of numerical simulation and experimental data are compared and analyzed.

  4. Investigation of retention and chiral recognition mechanism using quantitative structure-enantioselectivity retention relationship in high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    CHEN, Hui; LU, Xian-Yu; GAO, Ru-Yu; HUANG, Jun-Min; YANG, Hua-Zheng; WANG, Qin-Sun


    The enantiomers of a series of fourteen O-ethyl O-(substituted) phenyl N-isopropyl-phosphoroamidothioates have been separated by high performance liquid chromatography (HPLC) on the Pirkde-type chiral stationary phase. Seven molecular descriptors were lculated and four .significant descriptors were chosen to correlate against the experimental Ink′ values in order to form thequantitative structure-enantioselectivity retention relationships (QSERRs). Through the QSERRs, the retention and enantioselectivity meehanism were examined.

  5. The effect of moisture on the structures and properties of lead halide perovskites: a first-principles theoretical investigation. (United States)

    Zhang, Lei; Ju, Ming-Gang; Liang, WanZhen


    With efficiencies exceeding 20% and low production costs, lead halide perovskite solar cells (PSCs) have become potential candidates for future commercial applications. However, there are serious concerns about their long-term stability and environmental friendliness, heavily related to their commercial viability. Herein, we present a theoretical investigation based on the ab initio molecular dynamics (AIMD) simulations and the first-principles density functional theory (DFT) calculations to investigate the effects of sunlight and moisture on the structures and properties of MAPbI3 perovskites. AIMD simulations have been performed to simulate the impact of a few water molecules on the structures of MAPbI3 surfaces terminated in three different ways. The evolution of geometric and electronic structures as well as the absorption spectra has been shown. It is found that the PbI2-terminated surface is the most stable while both the MAI-terminated and PbI2-defective surfaces undergo structural reconstruction, leading to the formation of hydrated compounds in a humid environment. The moisture-induced weakening of photoabsorption is closely related to the formation of hydrated species, and the hydrated crystals MAPbI3·H2O and MA4PbI6·2H2O scarcely absorb the visible light. The electronic excitation in the bare and water-absorbed MAPbI3 nanoparticles tends to weaken Pb-I bonds, especially those around water molecules, and the maximal decrease of photoexcitation-induced bond order can reach up to 20% in the excited state in which the water molecules are involved in the electronic excitation, indicating the accelerated decomposition of perovskites in the presence of sunlight and moisture. This work is valuable for understanding the mechanism of chemical or photochemical instability of MAPbI3 perovskites in the presence of moisture.

  6. An Undergraduate Column Chromatography Experiment. (United States)

    Danot, M.; And Others


    Background information, list of materials needed, and procedures used are provided for an experiment designed to introduce undergraduate students to the theoretical and technical aspects of column chromatography. The experiment can also be shortened to serve as a demonstration of the column chromatography technique. (JN)

  7. Theoretical investigation of nonlinear resonances in a carbon nanotube cantilever with a tip-mass under electrostatic excitation (United States)

    Kim, I. K.; Lee, S. I.


    The nonlinear dynamics of a resonating carbon nanotube (CNT) cantilever having an attached mass at the tip ("tip mass") were investigated by incorporating electrostatic forces and intermolecular interactions between the CNT and a conducting plane surface. This work enables applications of CNT resonating sensors for tiny mass detection and provides a better understanding of the dynamics of CNT cantilevers. The effect of tip mass on a resonating CNT cantilever is normally characterized by the fundamental frequency shift in the linear resonance regime. However, there are more complex dynamics in the nonlinear resonance regime, such as secondary resonances with parametric excitation. The latter have been limited to nano-cantilevers without tip mass or to axially excited micro-beams. To analyze the nonlinear dynamics, we developed a differential equation model that includes both geometric and inertial nonlinear terms for the large vibration amplitudes at increasing drive forces. In our approach, we used Galerkin discretization techniques and numerical integration methods. The CNT cantilever exhibited complex nonlinear responses due to the applied AC and DC voltages and various tip masses. The nonlinear model had a softer response for increasing tip mass than those of the linear model with the same driving conditions. At low applied voltages, the cantilever had linear amplitude and phase responses at primary and secondary superharmonic resonance frequencies. The response branches were softened at the primary resonance through saddle-node (SN) bifurcation from harmonic electrostatic excitation at higher applied voltages. After SN bifurcation, the lower branch of the solution near resonance became unstable. In addition, theoretical analyses were performed on more complex nonlinear responses and stability changes with tip mass variations, such as period-doubling (PD) bifurcation at subharmonic resonance frequencies.

  8. Bonding, Structure, and Stability of Clusters: Some Surprising Results from an Experimental and Theoretical Investigation in Gas Phase

    Directory of Open Access Journals (Sweden)

    Melissa S. Caetano


    Full Text Available Structure and stability of clusters in the ground state were analyzed at the theoretical and experimental levels. Our experimental and theoretical findings showed that the clusters in gas phase tend to form mainly planar rings of four members. The symmetry and the small dipole moment in these specific configurations suggested that their stability could be associated with an alignment of the water molecules, maximizing attractive electrostatic interactions caused by changes in the charge distribution of the clusters.

  9. Ion and gas chromatography mass spectrometry investigations of organophosphates in lithium ion battery electrolytes by electrochemical aging at elevated cathode potentials (United States)

    Weber, Waldemar; Wagner, Ralf; Streipert, Benjamin; Kraft, Vadim; Winter, Martin; Nowak, Sascha


    The electrochemical aging of commercial non-aqueous lithium hexafluorophosphate (LiPF6)/organic carbonate solvent based lithium ion battery electrolyte has been investigated in view of the formation of ionic and non-ionic alkylated phosphates. Subject was a solvent mixture of ethylene carbonate/ethyl methyl carbonate EC:EMC (1:1, by wt.) with 1 M LiPF6 (LP50 Selectilyte™, BASF). The analysis was carried out by ion chromatography coupled with electrospray ionization mass spectrometry (ESI-MS) for ionic compounds and (headspace) gas chromatography mass spectrometry ((HS)-GC-MS) for non-ionic compounds. The electrochemical aging was performed by galvanostatic charge/discharge cycling and potentiostatic experiments with LiNi0.5Mn1.5O4 (LMNO) as cathode material at increased cut-off potentials (>4.5 V vs. Li/Li+). A strong dependence of the formation of organophosphates on the applied electrode potential was observed and investigated by quantitative analysis of the formed phosphates. In addition, new possible "fingerprint" compounds for describing the electrolyte status were investigated and compared to existing compounds.

  10. Theoretical Investigation of Dynamic Properties of Magnetic Molecule Systems as Probed by NMR and Pulsed Fields Experiments

    Energy Technology Data Exchange (ETDEWEB)

    Rousochatzakis, Ioannis [Iowa State Univ., Ames, IA (United States)


    The field of molecular magnetism[l-6] has become a subject of intense theoretical and experimental interest and has rapidly evolved during the last years. This inter-disciplinary field concerns magnetic systems at the molecular or "nanoscopic" level, whose realization has become feasible due to recent advances in the field of chemical synthesis. The present theoretical work provides a first step towards exploiting the possibilities that are offered by probing magnetic molecules using external magnetic fields with high sweep rates. These probes, apart for providing information specific to magnetic molecules, offer the possibility of conducting a detailed study of the relaxational behavior of interacting spin systems as a result of their coupling with a "heat bath" and in particular the excitations of the host lattice. Development of a broad theoretical framework for dealing with relaxational phenomena induced by dynamical magnetic fields is indeed a worthy goal.

  11. Theoretical and experimental investigation of drug-polymer interaction and miscibility and its impact on drug supersaturation in aqueous medium. (United States)

    Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J


    Amorphous solid dispersions (ASDs) have the potential to offer higher apparent solubility and bioavailability of BCS class II drugs. Knowledge of the solid state drug-polymer solubility/miscibility and their mutual interaction are fundamental requirements for the effective design and development of such systems. To this end, we have carried out a comprehensive investigation of various ASD systems of dipyridamole and cinnarizine in polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) at different drug loadings. Theoretical and experimental examinations (by implementing binary and ternary Flory-Huggins (F-H) theory) related to drug-polymer interaction/miscibility including solubility parameter approach, melting point depression method, phase diagram, drug-polymer interaction in the presence of moisture and the effect of drug loading on interaction parameter were performed. The information obtained from this study was used to predict the stability of ASDs at different drug loadings and under different thermal and moisture conditions. Thermal and moisture sorption analysis not only provided the composition-dependent interaction parameter but also predicted the composition dependent miscibility. DPM-PVP, DPM-PAA and CNZ-PAA systems have shown molecular level mixing over the complete range of drug loading. For CNZ-PVP, the presence of a single Tg at lower drug loadings (10, 20 and 35%w/w) indicates the formation of solid solution. However, drug recrystallization was observed for samples with higher drug weight fractions (50 and 65%w/w). Finally, the role of polymer in maintaining drug supersaturation has also been explored. It has been found that drug-polymer combinations capable of hydrogen-bonding in the solution state (DPM-PVP, DPM-PAA and CNZ-PAA) are more effective in preventing drug crystallization compared to the drug-polymer systems without such interaction (CNZ-PVP). The DPM-PAA system outperformed all other ASDs in various stability conditions (dry-state, in

  12. Amino acid-type interactions of L-3,4-dihydroxyphenylalanine with transition metal ions: An experimental and theoretical investigation (United States)

    Mandal, Shilpi; Das, Gunajyoti; Askari, Hassan


    This paper reports the synthesis of the Ni+2, Cu+2 and Zn+2 complexes of L-3,4-dihydroxyphenylalanine (L-dopa) using a solvent-free solid-state grinding procedure. The synthesized complexes are characterized by elemental, molar conductance, EDAX-SEM, TG/DTA, infrared, electronic absorption, fluorescence and XRD analyses; confirming a 1:2 metal-ligand stoichiometry of the complexes and involvement of the carboxyl and amino groups in complex formation. Phase-diagram and the kinetic parameters of the interactions between L-dopa and the metal ions are also explored. Molecular structures of the metal complexes are modeled within the framework of density functional theory in a vacuum and implicit aqueous environment using the most stable L-dopa conformers determined at the MP2/6-311++G(d,p) level. The gas and aqueous phase metal-binding affinities; theoretical IR and UV-vis spectral aspects; partial atomic charges; Wiberg bond indices; HOMO-LUMO energy gaps and dipole moments of the L-dopa conformers as well as their complexes are calculated and analyzed at B3LYP/6-311++G(d,p) level. The singlet state of the Ni(L-dopa)2 complex is found to be more favorable from thermodynamic perspectives as compared to the triplet state. Use of BHandHLYP and dispersion-corrected B3LYP (at DFT-D2 level) methods in conjugation with the 6-311++G(d,p) basis set affords us to accurately predict the binding affinity order of the three Lewis acids investigated, assess the influence of metal-aromatic π interactions on the thermodynamic stability of metalated L-dopa, and explore the effectiveness of the aforesaid methodologies in predicting a certain set of spectral and electronic properties of bioactive molecules. UV-vis titration and docking studies reveal that the metal complexes of L-dopa are able to bind to the surface of DNA.

  13. Hydrophobic noncovalent interactions of inosine-phenylalanine: a theoretical model for investigating the molecular recognition of nucleobases. (United States)

    Santos, Lucas A; da Cunha, Elaine F F; Freitas, Matheus P; Ramalho, Teodorico C


    Understanding the molecular recognition process of nucleobases is one of the greatest challenges for both computational chemistry and biophysics fields. In fact, our results point out that it is a hard task to take into account the hydrophobic interactions, such as π-π and T-stacking interactions, by theoretical calculations using conventional force fields due to quantum effects of hyperconjugation and electronic correlation. In this line, our findings put in evidence that simple modifications in the Lennard-Jones potential can improve theoretical predictions in scenarios where hydrophobic interactions can drive the molecular recognition.

  14. Theoretical investigation on thermal performance of heat pipe flat plate solar collector with cross flow heat exchanger (United States)

    Xiao, Lan; Wu, Shuang-Ying; Zhang, Qiao-Ling; Li, You-Rong


    Based on the heat transfer characteristics of absorber plate and the heat transfer effectiveness-number of heat transfer unit method of heat exchanger, a new theoretical method of analyzing the thermal performance of heat pipe flat plate solar collector with cross flow heat exchanger has been put forward and validated by comparisons with the experimental and numerical results in pre-existing literature. The proposed theoretical method can be used to analyze and discuss the influence of relevant parameters on the thermal performance of heat pipe flat plate solar collector.

  15. Discrimination of eight chloramphenicol isomers by liquid chromatography tandem mass spectrometry in order to investigate the natural occurrence of chloramphenicol. (United States)

    Berendsen, Bjorn J A; Zuidema, Tina; de Jong, Jacob; Stolker, Linda A A M; Nielen, Michel W F


    This paper describes the discrimination of eight different isomers of chloramphenicol (CAP), an antibiotic banned for use in food producing animals, by reversed phase and chiral liquid chromatography in combination with tandem mass spectrometric detection. Previously, by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) the presence of CAP was confirmed in some grass and herb samples collected on Mongolian pastures up to concentrations of 450 μg kg(-1). It was not possible to establish the cause of CAP residues which has initiated research on the natural occurrence of this drug. CAP occurs in the para-configuration and in the meta-configuration and contains two chiral centers thus eight different isomeric configurations exist, namely four (RR, SS, RS, SR) meta-stereoisomers and four para-stereoisomers. It is known that only RR-p-CAP has antimicrobial properties. To find out if the CAP detected in the plant material samples is the active configuration, a high resolution reversed phase LC-MS/MS system was tested for its ability to separate the different isomers. This system proved to be able to discriminate between some isomers, but not between RR-p-CAP and SS-p-CAP, also called dextramycin. Despite a detailed elucidation of the product ions and the fragmentation patterns of all isomers, MS/MS did not add sufficient specificity for full discrimination of the isomers. Therefore a chiral liquid chromatographic separation with MS/MS detection that is able to distinguish all isomers was developed and finally the isomeric ratio of non-compliant plant material samples and some CAP formulations was determined using this system. This showed that Mongolian grass and herb samples only contain the biological active isomer of CAP as do the obtained formulations. Therefore the CAP present in the plant material might origin from the production by soil organisms or from a manufactured source.

  16. Neuere Chromatographie (United States)

    Hostettmann, K.


    Besides high-performance liquid chromatography (HPLC) which is now a well-established and currently used technique, several emerging methods for the isolation and separation of natural products are receiving considerable attention. Centrifugal thin-layer chromatography is a very rapid technique, but limited in resolution. Of special interest are the recently developed support-free liquid-liquid chromatography methods such as droplet counter-current chromatography (DCCC) and rotation locular counter-current chromatography (RLCC). This latter method was applied to the separation of the enantiomers of (±)-norephedrine.

  17. Electronic properties and 4f→ 5d transitions in Ce-doped Lu2SiO5: a theoretical investigation


    Ning, Lixin; Lin, Lihua; Li, Lanlan; Wu, Changbao; Duan, Chang-Kui; Zhang, Yongfan; Seijo, Luis


    This is an electronic version of an article published in Journal of Materials Chemistry. Ning, L., Lin, L., Li, L., Wu, C., Duan, C., Zhang, Y. and Luis Seijo. "Electronic properties and 4f 5d transitions in Ce-doped Lu2SiO5: a theoretical investigation". Journal of Materials Chemistry 22 (2012): 13723-13731

  18. Multiscale atomistic simulation of metal-oxygen surface interactions: Methodological development, theoretical investigation, and correlation with experiment

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Judith C. [Univ. of Pittsburgh, Pittsburgh, PA (United States)


    The purpose of this grant is to develop the multi-scale theoretical methods to describe the nanoscale oxidation of metal thin films, as the PI (Yang) extensive previous experience in the experimental elucidation of the initial stages of Cu oxidation by primarily in situ transmission electron microscopy methods. Through the use and development of computational tools at varying length (and time) scales, from atomistic quantum mechanical calculation, force field mesoscale simulations, to large scale Kinetic Monte Carlo (KMC) modeling, the fundamental underpinings of the initial stages of Cu oxidation have been elucidated. The development of computational modeling tools allows for accelerated materials discovery. The theoretical tools developed from this program impact a wide range of technologies that depend on surface reactions, including corrosion, catalysis, and nanomaterials fabrication.

  19. Design theory and experimental investigation of the low frequency and high power rare earth magnetostrictive flextensional transducer (I). Theoretical part

    Institute of Scientific and Technical Information of China (English)

    HE Xiping; SUN Jincai; LI Bin


    The energy relationships among all the elements, by which the magnetostrictive transducers are manufactured, in Finite Element Method (FEM) are analyzed, then the expressions of FEM dynamics equations and performances formulas for magnetostrictive transducers are derived. The vibrating modes of the class VII transducer and its shell vibration are calculated theoretically and the results point out that there is a breathing mode and if the transducer works at this mode, the transducer will vibrate with a greater volume speed and source level.

  20. Micellar Electrokinetic Chromatography (United States)

    Bald, Edward; Kubalczyk, Paweł

    Since the introduction of micellar electrokinetic chromatography by Terabe, several authors have paid attention to the fundamental characteristics of this separation method. In this chapter the theoretical and practical aspects of resolution optimization, as well as the effect of different separation parameters on the migration behavior are discussed. These among others include fundamentals of separation, retention factor and resolution equation, efficiency, selectivity, and various surfactants and additives. Initial conditions for method development and instrumental approaches such as mass spectrometry detection are also mentioned covering the proposals for overcoming the difficulties arising from the coupling micellar electrokinetic chromatography with mass spectrometry detection.

  1. Theoretical investigation of the optical and EPR parameters for VO{sup 2+}ion in some complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kalfaoglu, Emel [OndokuzMay Latin-Small-Letter-Dotless-I s University, Faculty of Sciences, Department of Physics, 55139 Kurupelit-Samsun (Turkey); Karabulut, Buenyamin, E-mail: [OndokuzMay Latin-Small-Letter-Dotless-I s University, Faculty of Sciences, Department of Physics, 55139 Kurupelit-Samsun (Turkey)


    The molecular orbital coefficients and the EPR parameters of trisodium citrate dihydrate, sodium hydrogen oxalate monohydrate, potassium d-gluconate monohydrate and L-Alanine vanadyl complexes are calculated theoretically. Two d-d transition spectra and EPR parameters for the VO{sup 2+} complex are calculated theoretically by using crystal-field theory. The calculated g and A paramaters have indicated that paramagnetic center is axially symmetric. Having the relations of g{sub Parallel-To } Left-Pointing-Angle-Bracket g{sub Up-Tack } Left-Pointing-Angle-Bracket g{sub e} and A{sub Parallel-To } Right-Pointing-Angle-Bracket A{sub Up-Tack} for VO{sup 2+} ions, it can be concluded that VO{sup 2+} ions are located in distorted octahedral sites (C{sub 4v}) elongated along the z-axis and the ground state of the paramagnetic electron is d{sub xy}. - Highlights: Black-Right-Pointing-Pointer The EPR parameters and molecular orbital coefficients are calculated theoretically. Black-Right-Pointing-Pointer The g and A values of all complexes are found to be nearly axially symmetric. Black-Right-Pointing-Pointer The ground state of the paramagnetic electron is d{sub xy.}.

  2. A Theoretical Investigation of the Structure and Reactivity of the Molecular Constituents of Oil Sand and Oil Shale

    Energy Technology Data Exchange (ETDEWEB)

    Parish, Carol A. [Univ. of Richmond, VA (United States)


    2 reaction at three different sites on the 2-thienylmethyl radical. The addition is exothermic by 37 ~ 55 kcal mol-1 relative to the entrance channel. These excess energies are available to promote further decomposition or rearrangement of the adducts that lead to nascent products such as H, OH, H2O and CH2O. The reaction surfaces are characterized by relatively low barriers (most are lower than 10 kcal mol-1). Based upon a careful analysis of the overall barrier heights and reaction exothermicities, the formation of O2, OH and H2O is likely to be an important pathway in the radical recombination reactions of 2-thienylmethyl + HO2. This work was published in the Journal of Physical Chemistry A, 2011, 115, 14546-14557. REACTION OF THIOPHENE AND METHYLTHIOPHENE WITH SINGLET AND TRIPLET MOLECULAR OXYGEN Mechanisms for the reaction of thiophene and 2-methylthiophene with molecular oxygen on both the triplet and singlet potential energy surfaces (PESs) were investigated using ab initio methods. Thiophene and 2-methylthiophene where shown to react with O2 via two types of mechanisms; namely, direct hydrogen abstraction and addition/elimination. The barriers for reaction with triplet oxygen are all significantly large (i.e., > 30 kcal mol-1), which indicates that the direct oxidation of thiophene by ground state oxygen might be important only in high temperature processes. Reaction of thiophene with singlet oxygen via a 2+4 cycloaddition leading to endoperoxides is the most favorable channel. Moreover, it was found that alkylation of the thiophene ring (i.e., methyl-substituted thiophene) is capable of lowering the barrier height for the addition pathway. The implication of the current theoretical results may shed new light on the initiation mechanisms for combustion of asphaltenes. This work was published in the Journal of Physical Chemistry A, 2012 116, 4934-4946. JAHN-TELLER STABILIZATION IN POSS CATIONS We have a long

  3. Numerical investigation into the effects of ordered particle packing and slip flow on the performance of chromatography. (United States)

    Yan, Xiaohong; Wang, Qiuwang


    The pressure drop and the plate height of chromatography columns packed with particles in the face-centered cubic, the body-centered cubic and the simple cubic configurations are calculated by a volume averaging method model. It is found that the Kozeny-Carman equation provides a reasonable prediction of the pressure drop when particles are in the face-centered cubic configuration, but overestimates the pressure drop when particles are in the body-centered cubic and the simple cubic configurations. The face-centered cubic configuration has the advantage to provide a smaller longitudinal dispersion coefficient than the body-centered cubic, the simple cubic, and the random configurations. The pressure drop and the plate height for slip flow through particles in the face-centered cubic configuration are lower than that for no-slip flow. The values of the smallest reduced plate height of columns packed with particles in the face-centered cubic configuration for no-slip flow and slip flow are about 0.084 and 0.059, respectively. The plate height of the ordered particle packing structures is smaller and the effect of slip flow on the plate height is less remarkable than results reported in literature.

  4. Investigation of pharmaceuticals in processed animal by-products by liquid chromatography coupled to high-resolution mass spectrometry. (United States)

    Nácher-Mestre, Jaime; Ibáñez, María; Serrano, Roque; Boix, Clara; Bijlsma, Lubertus; Lunestad, Bjørn Tore; Hannisdal, Rita; Alm, Martin; Hernández, Félix; Berntssen, Marc H G


    There is an on-going trend for developing more sustainable salmon feed in which traditionally applied marine feed ingredients are replaced with alternatives. Processed animal products (PAPs) have been re-authorized as novel high quality protein ingredients in 2013. These PAPs may harbor undesirable substances such as pharmaceuticals and metabolites which are not previously associated with salmon farming, but might cause a potential risk for feed and food safety. To control these contaminants, an analytical strategy based on a generic extraction followed by ultra-high performance liquid chromatography coupled to high resolution mass spectrometry (UHPLC-HRMS) using quadrupole time-of-flight mass analyzer (QTOF MS) was applied for wide scope screening. Quality control samples, consisting of PAP commodities spiked at 0.02, 0.1 and 0.2 mg/kg with 150 analytes, were injected in every sample batch to verify the overall method performance. The methodology was applied to 19 commercially available PAP samples from six different types of matrices from the EU animal rendering industry. This strategy allows assessing possible emergent risk exposition of the salmon farming industry to 1005 undesirables, including pharmaceuticals, several dyes and relevant metabolites.

  5. Surface Energy Determined by Inverse Gas Chromatography as a Tool to Investigate Particulate Interactions in Dry Powder Inhalers. (United States)

    Das, Shyamal C; Tucker, Ian G; Stewart, Peter J


    Dry powder inhalers (DPIs) usually contain drug particles energy of particles. Inverse gas chromatography (IGC) has been used to determine the surface energy of powder particles used in DPI to characterize materials and to understand aerosolization behaviour. Early studies used an infinite dilution technique to determine nonpolar surface energy and free energy of adsorption for polar interactions separately. Although some correlations were observed with the change in nonpolar surface energy before and after micronization, milling and storage, a lack of consistency in the change of free energy of adsorption was common. Moreover, a consistent relationship between complex de-agglomeration behaviour and surface energy has not been established and there are even some examples of negative correlation. In fact, nonpolar surface energy at infinite dilution is an incomplete representation of powder surface characteristics. The techniques for measuring polar surface energy, total surface energy and surface energy distribution have provided more revealing information about surface energetics of powders. Surface energy distributions determined by IGC or surface energy analyser have been successfully used to understand energetic heterogeneity of surfaces, characterize different polymorphs and understand changes due to micronization, structural relaxation, dry coating and storage. Efforts have been made to utilize surface energy distribution data to calculate powder strength distribution and to explain complex de-agglomeration behaviour of DPI formulations.

  6. Investigation of a fusion technique for the determination of total sulfur in geological samples by ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Stallings, E.A.; Candelaria, L.M.; Gladney, E.S.


    The authors have encountered the need for a rapid, accurate, precise, and sensitive method for measuring total sulfur in large numbers of geological samples. Numerous environmental studies of sulfur deposition due to sulfur dioxide emission from combustion and industry are currently under way. Several techniques for measuring total sulfur in soils and other silicate materials have been published including neutron activation analysis, thermal neutron capture prompt ..gamma..-ray spectrometry, inductively coupled plasma atomic emission spectrometry, isotope dilution mass spectrometry, X-ray fluorescence, turbidimetry, ion chromatography (IC), iodimetric titration, and fluorometry. However, none of these methods is completely satisfactory for routine analysis of large numbers of samples. Many have levels of detection that are inadequate for measuring low levels of total sulfur (<100 often encountered in soils. Several utilize only aqueous extracts of the soils and do not provide a total sulfur determination. Others require extensive sample preparation, are susceptible to loss of sulfur during oxidation, or produce incomplete conversion of sulfur species to sulfate. The objective of this work was to evaluate the accuracy of IC determination of sulfate for Na/sub 2/O/sub 2/ soil fusions by comparing the results obtained for reference materials with literature values reported for other techniques. They were also interested in determining if this fusion method would be rapid enough to handle large numbers of samples.

  7. Investigating effects of sample pretreatment on protein stability using size-exclusion chromatography and high-resolution continuum source atomic absorption spectrometry. (United States)

    Rakow, Tobias; El Deeb, Sami; Hahne, Thomas; El-Hady, Deia Abd; AlBishri, Hassan M; Wätzig, Hermann


    In this study, size-exclusion chromatography and high-resolution atomic absorption spectrometry methods have been developed and evaluated to test the stability of proteins during sample pretreatment. This especially includes different storage conditions but also adsorption before or even during the chromatographic process. For the development of the size exclusion method, a Biosep S3000 5 μm column was used for investigating a series of representative model proteins, namely bovine serum albumin, ovalbumin, monoclonal immunoglobulin G antibody, and myoglobin. Ambient temperature storage was found to be harmful to all model proteins, whereas short-term storage up to 14 days could be done in an ordinary refrigerator. Freezing the protein solutions was always complicated and had to be evaluated for each protein in the corresponding solvent. To keep the proteins in their native state a gentle freezing temperature should be chosen, hence liquid nitrogen should be avoided. Furthermore, a high-resolution continuum source atomic absorption spectrometry method was developed to observe the adsorption of proteins on container material and chromatographic columns. Adsorption to any container led to a sample loss and lowered the recovery rates. During the pretreatment and high-performance size-exclusion chromatography, adsorption caused sample losses of up to 33%.

  8. Theoretical investigations on optical properties of magneto-optical thin film on ion-exchanged glass waveguide (United States)

    Hocini, Abdesselam; Bouras, Mounir; Amata, Hadi


    In this work, we report on the theoretical study of magneto-optical waveguides on an ion-exchanged glass waveguide, this latter is made by sol-gel process and doped with magnetic nanoparticles with two kinds of matrix (SiO2/TiO2 and SiO2/ZrO2). The mode propagation and the lateral light confinement for both polarizations TE and TM are simulated using software based on a film mode matching method. We propose from those results magneto-optical waveguides on ion-exchanged glass waveguide geometries for optical integrated applications.

  9. Theoretical and Experimental Investigation of Flexural Wave Propagating in a Periodic Pipe with Fluid-Filled Loading

    Institute of Scientific and Technical Information of China (English)

    WEN Ji-Hong; SHEN Hui-Jie; YU Dian-Long; WEN Xi-Sen


    @@ Based on the Bragg scattering mechanism of phononic crystals(PCs),a periodic composite material pipe with fluid loading is designed and studied.The band structure of the flexural wave in the periodic pipe is calculated with the transfer matrix(TM)method.A periodic piping experimental system is designed,and the vibration experiment is performed to validate the attenuation ability of the periodic pipe structure.Finally,a finiteelement pipe model is constructed using the MSC-Actran software,and the calculated results match well with the vibration experiment.The errors between the theoretical calculation results and the vibration experimental results are analyzed.

  10. Of Chains and Rings: Synthetic Strategies and Theoretical Investigations for Tuning the Structure of Silver Coordination Compounds and Their Applications

    Directory of Open Access Journals (Sweden)

    Tünde Vig Slenters


    Full Text Available Varying the polyethyleneglycol spacer between two (iso-nicotinic groups of the ligand systems, a large structural variety of silver coordination compounds was obtained, starting with zero-dimensional ring systems, via one-dimensional chains, helices and double-helices to two-dimensional polycatenanes. Theoretical calculations help to understand their formation and allow predictions in some cases. These structures can be tuned by careful design of the ligand, the use of solvent and the counter ions, influencing also other important properties such as light stability and solubility. The latter is important in the context of biomedical applications, using silver compounds as antimicrobial agents.

  11. Investigation of sound field for a standing wave tube system with flow and with lateral Helmholtz resonator Ⅰ. Theoretical analysis

    Institute of Scientific and Technical Information of China (English)

    LIU Ke; LI Song; GUO Qing; HUANG Dongtao


    A lateral Helmholtz resonator added to a standing wave tube without flow has been validated as a method of noise reduction for combustion noise radiated from combustion channel of rockets or turbines. But in fact there is a flow with low velocity in the combustion channel. Therefore the theoretical analysis carried out is aimed at sound field of standing wave tube with flow and with lateral Helmholtz resonator. Certainly a relevant math-physical model should first be formulated. Here three key problems need to be solved: (1) To formulate the discontinuity condition at the joint between the standing wave tube and Helmholtz resonator in the case of flow. (2) To determine the acoustic impedance of Helnholtz resonator, considering the effects of flow, viscous and multihole. (3) To formulate the reflection condition at the end of the standing wave tube. Some formulas for analysis of the sound field in the tube with flow and with lateral Helmholtz resonator are deduced. These theoretical works have been validated by experiments.

  12. Games and Diabetes: A Review Investigating Theoretical Frameworks, Evaluation Methodologies, and Opportunities for Design Grounded in Learning Theories. (United States)

    Lazem, Shaimaa; Webster, Mary; Holmes, Wayne; Wolf, Motje


    Here we review 18 articles that describe the design and evaluation of 1 or more games for diabetes from technical, methodological, and theoretical perspectives. We undertook searches covering the period 2010 to May 2015 in the ACM, IEEE, Journal of Medical Internet Research, Studies in Health Technology and Informatics, and Google Scholar online databases using the keywords "children," "computer games," "diabetes," "games," "type 1," and "type 2" in various Boolean combinations. The review sets out to establish, for future research, an understanding of the current landscape of digital games designed for children with diabetes. We briefly explored the use and impact of well-established learning theories in such games. The most frequently mentioned theoretical frameworks were social cognitive theory and social constructivism. Due to the limitations of the reported evaluation methodologies, little evidence was found to support the strong promise of games for diabetes. Furthermore, we could not establish a relation between design features and the game outcomes. We argue that an in-depth discussion about the extent to which learning theories could and should be manifested in the design decisions is required.

  13. Optimal electron irradiation as a tool for functionalization of MoS{sub 2}: Theoretical and experimental investigation

    Energy Technology Data Exchange (ETDEWEB)

    Karmakar, Debjani, E-mail:; Padma, N.; Ghosh, M.; Kaur, M.; Chandrasekhar Rao, T. V. [Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Halder, Rumu; Abraham, Geogy [Material Science Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Vaibhav, K. [Computer Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Bhattacharya, D. [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)


    We demonstrate the utility of electron irradiation as a tool to enhance device functionality of graphene-analogous MoS{sub 2}. With the help of first-principles based calculations, vacancy-induced changes of various electronic properties are shown to be a combined result of crystal-field modification and spin-orbital coupling. A comparative theoretical study of various possible vacancy configurations both in bulk and monolayer MoS{sub 2} and related changes in their respective band-structures help us to explain plausible irradiation induced effects. Experimentally, various structural forms of MoS{sub 2} in bulk, few layered flakes, and nanocrystals are observed to exhibit important modification of their magnetic, transport, and vibrational properties, following low doses of electron irradiation. While irradiated single crystals and nanocrystals show an enhanced magnetization, transport properties of few-layered devices show a significant increase in their conductivity, which can be very useful for fabrication of electronic devices. Our theoretical calculations reveal that this increase in n-type conductivity and magnetization can be correlated with the presence of sulfur and molybdenum vacancies.

  14. Theoretical and experimental investigation of magnetoelectric effect for bending-tension coupled modes in magnetostrictive-piezoelectric layered composites (United States)

    Hasanyan, D.; Gao, J.; Wang, Y.; Viswan, R.; Li, M.; Shen, Y.; Li, J.; Viehland, D.


    In this paper, we discuss a theoretical model with experimental verification for the resonance enhancement of magnetoelectric (ME) interactions at frequencies corresponding to bending-tension oscillations. A dynamic theory of arbitrary laminated magneto-elasto-electric bars was constructed. The model included bending and longitudinal vibration effects for predicting ME coefficients in laminate bar composite structures consisting of magnetostrictive, piezoelectric, and pure elastic layers. The thickness dependence of stress, strain, and magnetic and electric fields within a sample are taken into account, as such the bending deformations should be considered in an applied magnetic or electric field. The frequency dependence of the ME voltage coefficients has obtained by solving electrostatic, magnetostatic, and elastodynamic equations. We consider boundary conditions corresponding to free vibrations at both ends. As a demonstration, our theory for multilayer ME composites was then applied to ferromagnetic-ferroelectric bilayers, specifically Metglas-PZT ones. A theoretical model is presented for static (low-frequency) ME effects in such bilayers. We also performed experiments for these Metglas-PZT bilayers and analyzed the influence of Metglas geometry (length and thickness) and Metglas/PZT volume fraction on the ME coefficient. The frequency dependence of the ME coefficient is also presented for different geometries (length, thickness) of Metglas. The theory shows good agreement with experimental data, even near the resonance frequency.

  15. Spectroscopic and theoretical investigations of vibrational frequencies in binary unsaturated transition-metal carbonyl cations, neutrals, and anions. (United States)

    Zhou, M; Andrews, L; Bauschlicher, C W


    Figure 18 presents the C-O stretching vibrational frequencies of the first-row transition-metal monocarbonyl cations, neutrals, and anions in solid neon; similar diagrams have been reported for neutral MCO species in solid argon, but three of the early assignments have been changed by recent work and one new assignment added. The laser-ablation method produces mostly neutral atoms with a few percent cations and electrons for capture to make anions; in contrast, thermal evaporation gives only neutral species. Hence, the very recent neon matrix investigations in our laboratory provide carbonyl cations and anions for comparison to neutrals on a level playing field. Several trends are very interesting. First, for all metals, the C-O stretching frequencies follow the order cations > neutrals > anions with large diagnostic 100-200 cm-1 separations, which is consistent with the magnitude of the metal d to CO pi * donation. Second, for a given charge, there is a general increase in C-O stretching vibrational frequencies with increasing metal atomic number, which demonstrates the expected decrease in the metal to CO pi * donation with increasing metal ionization potential. Some of the structure in this plot arises from the extra stability of the filled and half-filled d shell and from the electron pairing that occurs at the middle of the TM row; the plot resembles the "double-humped" graph found for the variation in properties across a row of transition metals. For the anions, the variation with metal atom is the smallest since all of the metals can easily donate charge to the CO ligand. Third, for the early transition-metal Ti, V, and Cr families, the C-O stretching frequencies decrease when going down the family, but the reverse relationship is observed for the late transition-metal Fe, Co, and Ni families. In most of the present discussion, we have referred to neon matrix frequencies; however, the argon matrix frequencies are complementary, and useful information can be

  16. Using Affinity Chromatography to Investigate Novel Protein-Protein Interactions in an Undergraduate Cell and Molecular Biology Lab Course (United States)

    Belanger, Kenneth D.


    Inquiry-driven lab exercises require students to think carefully about a question, carry out an investigation of that question, and critically analyze the results of their investigation. Here, we describe the implementation and assessment of an inquiry-based laboratory exercise in which students obtain and analyze novel data that contribute to our…

  17. Theoretical investigations on magnetic entropy change in amorphous and crystalline systems: Applications to RAg (R=Tb, Dy, Ho) and GdCuAl

    Energy Technology Data Exchange (ETDEWEB)

    Ranke, P.J. von, E-mail: [Instituto de Física, Universidade do Estado do Rio de Janeiro – UERJ, Rua São Francisco Xavier, 524, 20550-013 RJ (Brazil); Nóbrega, E.P. [Instituto de Física, Universidade do Estado do Rio de Janeiro – UERJ, Rua São Francisco Xavier, 524, 20550-013 RJ (Brazil); Caldas, A. [Sociedade Unificada de Ensino Superior e Cultura, SUESC, 20211-351 Rio de Janeiro, RJ (Brazil); Alho, B.P. [Instituto de Aplicação Fernando Rodrigues da Silveira, Universidade do Estado do Rio de Janeiro, Rua Santa Alexandrina, 288, 20260-232 RJ (Brazil); Ribeiro, P.O.; Alvarenga, T.S.T.; Lopes, P.H.O.; Sousa, V.S.R. de [Instituto de Física, Universidade do Estado do Rio de Janeiro – UERJ, Rua São Francisco Xavier, 524, 20550-013 RJ (Brazil); Carvalho, A. Magnus G. [Laboratório Nacional de Luz Síncrotron, CNPEM, 13083-970 Campinas, SP (Brazil); Oliveira, N.A. de [Instituto de Física, Universidade do Estado do Rio de Janeiro – UERJ, Rua São Francisco Xavier, 524, 20550-013 RJ (Brazil)


    We report theoretical investigations on the magnetic entropy changes in amorphous systems through two different assumptions. In the first assumption, the HPZ-anisotropic model is considered to deal with the random direction of magnetic moments, where the amorphous RAg (R=Tb, Dy and Ho) were used as prototypes systems. In the second assumption, the amorphisation is parameterized through the exchange interaction distribution and GdCuAl, in amorphous and crystalline structures, were considered as prototypes systems. Comparisons between the magnetic entropy changes under amorphisation and under the usual magnetic field variation were performed. The model reveals the dependence of refrigerant capacity on the amorphisation parameter, and an optimum amorphisation parameter was calculated. - Highlights: • Theoretical investigation on RAg (R=Tb, Dy and Ho) and GdCuAl amorphous alloys. • Magnetic entropy changes in GdCuAl in both amorphous and crystalline structures. • The refrigerant capacity was compared in both amorphous and crystalline phases.

  18. Arsenic speciation in seafood samples with emphasis on minor constituents. An investigation by high performance liquid chromatography with inductively coupled plasma mass spectrometric detection

    DEFF Research Database (Denmark)

    Larsen, Erik Huusfeldt; Pritzl, G.; Hansen, S. H.


    Extracts of 11 samples of shrimp, crab, fish, fish liver, shellfish and lobster digestive gland (hepatopancreas), including five certified reference materials, were investigated for their contents of arsenic compounds (arsenic speciation). The cation-exchange high performance liquid chromatography...... procedure was optimized to separate six cationic arsenicals present in the samples with internal chromatographic standardization by the trimethylselenonium ion, which was detected a m/z 82 (Se-82), in addition to arsenic at m/z 75, by inductively coupled plasma mass spectrometry. The content of each species...... gland, and another unknown (U2) was present at 0.2-6.4% in all samples. The contents of arsenite and arsenate were 0-1.4%, dimethylarsinate 8.2-29% while monomethylarsonate was detected only in oyster at 0.3% of the total extracted arsenic. Finding tetramethylarsonium ion and arsenocholine in a variety...

  19. Investigation of a new core-shell particle column for ion-pair reversed-phase liquid chromatography analysis of oligonucleotides. (United States)

    Biba, Mirlinda; Welch, Christopher J; Foley, Joe P


    A new core-shell particle column showed excellent performance and durability for separation of short (∼21-mer) ribonucleic acid (RNA) oligonucleotides by ion-pair reversed-phase liquid chromatography (IP-RPLC). Previously investigated core-shell C18 columns showed excellent peak shapes and separations of closely eluting impurities by IP-RPLC. However, these columns showed only modest long-term stability at the neutral pH and elevated column temperatures of ≥60°C, typically used for IP-RPLC analysis of oligonucleotides. The newly introduced SunShell C18 column provided separations comparable to the previously evaluated core-shell columns, but with significantly improved long-term column stability when operated at neutral pH and elevated column temperature.

  20. A theoretical investigation of the laser damage threshold of metal multi-dielectric mirrors for high power ultrashort applications. (United States)

    Wang, Bin; Gallais, Laurent


    An approach for the theoretical evaluation of the damage threshold in optical interference coatings that combine metal and dielectric films is presented. The model that is used combines a matrix formalism to describe the film system with the two temperatures model that describes the energy transfer and the temperatures of electrons and lattice in a solid submitted to a laser irradiation at the femtosecond time scale. With this approach the thermal consequences due to the ultrafast absorption of the metal film can be evaluated in the multilayer stack for single or multiple pulses. Some applications are presented for the case of broadband mirrors for ultrashort pulses with low dispersion. Particularly we study the impact of the metal film (metal element, thickness) and the design on the Laser Induced Damage Threshold in the sub picosecond regime.

  1. A theoretical investigation on anomalous switching of single-stranded deoxyribonucleic acid (ssDNA) monolayers by water vapor

    Institute of Scientific and Technical Information of China (English)

    赵新军; 高志福; 蒋中英


    In this paper, we use a molecular theory to study the anomalous switching of ssDNA monolayers. Here, both ssDNA–water and water–water hydrogen bonds and their explicit coupling to the ssDNA conformations are considered. We find that hydrogen bonding becomes a key element in inducing the anomalous switching of ssDNA monolayers. This finding accords well with the experimental observations. Based on our theoretical model, we predict that the anomalous switching induced by water vapor will be applicable to a wide range of hydrogen bonds polymers, and ssDNA–water hydrogen bonds and water–water hydrogen bonds hybridization will lead to the hydrogen-bond network formation of 3D ssDNA monolayers.

  2. Experimental and theoretical investigation of the triple differential cross section for electron impact ionization of pyrimidine molecules. (United States)

    Builth-Williams, J D; Bellm, S M; Jones, D B; Chaluvadi, Hari; Madison, D H; Ning, C G; Lohmann, B; Brunger, M J


    Cross-section data for electron impact induced ionization of bio-molecules are important for modelling the deposition of energy within a biological medium and for gaining knowledge of electron driven processes at the molecular level. Triply differential cross sections have been measured for the electron impact ionization of the outer valence 7b(2) and 10a(1) orbitals of pyrimidine, using the (e, 2e) technique. The measurements have been performed with coplanar asymmetric kinematics, at an incident electron energy of 250 eV and ejected electron energy of 20 eV, for scattered electron angles of -5°, -10°, and -15°. The ejected electron angular range encompasses both the binary and recoil peaks in the triple differential cross section. Corresponding theoretical calculations have been performed using the molecular 3-body distorted wave model and are in reasonably good agreement with the present experiment.

  3. Synthesis, crystal structure, experimental and theoretical investigations of 3-(4-ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one (United States)

    Anam, Faiza; Abbas, Asghar; Lo, Kong Mun; Hameed, Shahid; Ramasami, Ponnadurai; Umar, Yunusa; Ullah, Aman; Naseer, Muhammad Moazzam


    A chalcone derivative namely, (E)-3-(4-ethoxy-3-methoxyphenyl)-1-phenylprop-2-en-1-one (1v) has been synthesized and characterized on the basis of its spectral data. The solid state self-assembly studies of 1v were carried out through single crystal X-ray technique to see the major non-covalent interactions responsible for molecular alignment in the solid state. Furthermore, the optimized molecular geometry, vibrational frequencies, 1H and 13C NMR chemical shift (in gas and in chloroform solvent) values and the molecular electrostatic potential (MEP) surface parameters of 1v were calculated using DFT/B3LYP/HF/M06 method with 6-311++G (d,p) basis set in ground state. All the theoretical calculations for 1v were found in good agreement with experimental data.

  4. Theoretical and experimental investigation of the mode-spacing of fiber Bragg grating Fabry-Perot cavity

    Institute of Scientific and Technical Information of China (English)

    Wenhua Ren; Peilin Tao; Zhongwei Tan; Yan Liu; Shuisheng Jian


    The mode-spacing of the fiber Bragg grating Fabry-Perot(FBG F-P)cavity is calculated by using the effective cavity length which contains the effective length of the FBG.The expression of the effective length,defined by using the phase-time delay,is obtained and simplified as a function of the peak reflectivity at the Bragg wavelength,the band edges,and the first zero-reflectivity wavelength.The effective length is discussed from the energy penetration depth point of view.Three FBG F-P cavities are fabricated in order to validate the effective length approach.The experimental data fits well with the theoretical predictions.The limitation of this method is also pointed out and the improved approach is proposed.

  5. Quantum Field-theoretical Investigations In Nonperturbative Qcd And Beyond-the-standard-model Electroweak Physics (lepton, Tau Lepton, Photon)

    CERN Document Server

    Xue, Y


    In this thesis, the lowest-order gluon condensate contributions to the QED vertex are calculated. The conclusions appear to be that the presence of a gluon condensate eliminates any possibility of an anomalous magnetic moment. Single instanton contributions to pseudo-scalar finite energy sum rules are derived both asymptotically and theoretically. The one- resonance finite energy sum rule fit in the scalar channel is explored, in an effort to see if such sum rules support the existence of a very light ($\\sigma$) scalar resonance. Cancellation of infrared singularities in two-gluon condensate contributions to finite energy sum rules are demonstrated not to be peculiar to the channels in which they are studied. The explicit cancellation of quark-mass singularities via operator mixing is also demonstrated for the channels in which they naively occur. The hard photon spectrum in radiative leptonic $\\tau$ decays $\\tau\\to \\mu\\bar\

  6. Developing a Theoretical Framework Using a Nursing Perspective to Investigate Perceived Health in the "Sandwich Generation" Group. (United States)

    Oulevey Bachmann, Annie; Danuser, Brigitta; Morin, Diane


    Coexisting workloads from professional, household and family, and caregiving activities for frail parents expose middle-aged individuals, the so-called "Sandwich Generation", to potential health risks. Current trends suggest that this situation will continue or increase. Thus SG health promotion has become a nursing concern. Most existing research considers coexisting workloads a priori pathogenic. Most studies have examined the association of one, versus two, of these three activities with health. Few studies have used a nursing perspective. This article presents the development of a framework based on a nursing model. We integrated Siegrist's Effort-Reward Imbalance middle-range theory into "Neuman Systems Model". The latter was chosen for its salutogenic orientation, its attention to preventive nursing interventions and the opportunity it provides to simultaneously consider positive and negative perceptions of SG health and SG coexisting workloads. Finally, it facilitated a theoretical identification of health protective factors.

  7. A FRAP model to investigate reaction-diffusion of proteins within a bounded domain: a theoretical approach

    CERN Document Server

    Tsibidis, George D


    Temporally and spatially resolved measurements of protein transport inside cells provide important clues to the functional architecture and dynamics of biological systems. Fluorescence Recovery After Photobleaching (FRAP) technique has been used over the past three decades to measure the mobility of macromolecules and protein transport and interaction with immobile structures inside the cell nucleus. A theoretical model is presented that aims to describe protein transport inside the nucleus, a process which is influenced by the presence of a boundary (i.e. membrane). A set of reaction-diffusion equations is employed to model both the diffusion of proteins and their interaction with immobile binding sites. The proposed model has been designed to be applied to biological samples with a Confocal Laser Scanning Microscope (CLSM) equipped with the feature to bleach regions characterised by a scanning beam that has a radially Gaussian distributed profile. The proposed model leads to FRAP curves that depend on the o...

  8. Theoretical investigation of new Heusler alloys Ru{sub 2}VGa{sub 1−x}Al{sub x}

    Energy Technology Data Exchange (ETDEWEB)

    Abbassa, Hamza [Département de Physique, Université de Abdelhamid Ibn Badis de Mostaganem, Mostaganem (Algeria); Laboratoire de Physique des Couches Minces et Matériaux pour l’Electronique (LPC2ME), Université d’Oran, Es-Senia, Oran (Algeria); Hadjri-Mebarki, Soria [Laboratoire de Physique des Couches Minces et Matériaux pour l’Electronique (LPC2ME), Université d’Oran, Es-Senia, Oran (Algeria); Amrani, Bouhalouane, E-mail: [Laboratoire de Physique des Couches Minces et Matériaux pour l’Electronique (LPC2ME), Université d’Oran, Es-Senia, Oran (Algeria); Belaroussi, Tayeb [Département de Physique, Université de Abdelhamid Ibn Badis de Mostaganem, Mostaganem (Algeria); Laboratoire de Physique de Plasmas des Matériaux Conducteur et leur Applications (LPPMCA), Université d’USTOMB, Oran (Algeria); Driss Khodja, Kouider [Laboratoire de Physique des Couches Minces et Matériaux pour l’Electronique (LPC2ME), Université d’Oran, Es-Senia, Oran (Algeria); Aubert, Pascal [Institut d’Electronique Fondamentale, Université Paris-Sud – CNRS, Orsay 91405 (France)


    Highlights: • Electronic and thermodynamic properties of new Heusler alloys Ru{sub 2}VGa{sub 1−x}Al{sub x} (x = 0, 0.25, 0.50, 0.75, and 1.00) are studied. • Elastic parameters and stability of Ru{sub 2}VGa{sub 1−x}Al{sub x} alloys. • A linear behavior of the lattice parameter, bulk modulus, elastic constants and Debye temperature on x has been observed. - Abstract: Results of first-principles full-potential linearized augmented plane wave calculations of elastic and related electronic and thermodynamic properties of the quaternary Heusler alloys Ru{sub 2}VAl{sub x}Ga{sub 1−x} (x = 0, 0.25, 0.5, 0.75, 1) are presented. These materials were found to have the L2{sub 1} structure for all concentrations. The agreement between the theoretical and experimental lattice parameters for both Ru{sub 2}VAl and Ru{sub 2}VGa at various temperatures was found to be satisfactory. Our results provide predictions for the remaining mixed more» Heusler alloys Ru{sub 2}VAl{sub x}Ga{sub 1−x} (0 < x < 1) for which no direct experimental or theoretical data are presently available. In their equilibrium L2{sub 1} structure, all concentrations are non-magnetic metals. A linear variation of the lattice parameter, bulk modulus, elastic constants and Debye temperature has been observed with x.

  9. Learning curves, taking instructions, and patient safety: using a theoretical domains framework in an interview study to investigate prescribing errors among trainee doctors

    Directory of Open Access Journals (Sweden)

    Duncan Eilidh M


    Full Text Available Abstract Background Prescribing errors are a major source of morbidity and mortality and represent a significant patient safety concern. Evidence suggests that trainee doctors are responsible for most prescribing errors. Understanding the factors that influence prescribing behavior may lead to effective interventions to reduce errors. Existing investigations of prescribing errors have been based on Human Error Theory but not on other relevant behavioral theories. The aim of this study was to apply a broad theory-based approach using the Theoretical Domains Framework (TDF to investigate prescribing in the hospital context among a sample of trainee doctors. Method Semistructured interviews, based on 12 theoretical domains, were conducted with 22 trainee doctors to explore views, opinions, and experiences of prescribing and prescribing errors. Content analysis was conducted, followed by applying relevance criteria and a novel stage of critical appraisal, to identify which theoretical domains could be targeted in interventions to improve prescribing. Results Seven theoretical domains met the criteria of relevance: “social professional role and identity,” “environmental context and resources,” “social influences,” “knowledge,” “skills,” “memory, attention, and decision making,” and “behavioral regulation.” From critical appraisal of the interview data, “beliefs about consequences” and “beliefs about capabilities” were also identified as potentially important domains. Interrelationships between domains were evident. Additionally, the data supported theoretical elaboration of the domain behavioral regulation. Conclusions In this investigation of hospital-based prescribing, participants’ attributions about causes of errors were used to identify domains that could be targeted in interventions to improve prescribing. In a departure from previous TDF practice, critical appraisal was used to identify additional domains

  10. Theoretical investigation on dual fluorescence and intramolecular charge transfer of 5-phenyl-5H-phenanthridin-6-one

    Institute of Scientific and Technical Information of China (English)


    Quantum-chemical calculations with the time-dependent density function theory (TDDFT) have been carried out for 5-phenyl-5H-phenanthridin-6-one (PP). For this molecule, dual fluorescence and in- tramolecular charge transfer (ICT) were experimentally observed. The B3LYP functional with 6-311+G (2d, p) basis set has been used for the theoretical calculations. The solvent effects have been described within the polarizable continuum model (PCM). Ground-state geometry optimization reveals that the phenyl/phenanthridinone dihedral angle equals 90.0°, a nearly perpendicular structure. Vertical ab- sorption energy calculations characterize the lower singlet excited states both in gas phase and in solvents. It can be found that the lower excited states have locally excitation (LE) feature. Through constructing the potential energy curves of both isolated and solvated systems describing the LE→ICT reaction and fluorescence emission, we obtain the enthalpy difference ΔH between the LE and ICT states, energy barrier Ea, and energy difference δEFC, indicating the structural changes taking place during the ICT reaction. Potential curve and calculated emission energies for both isolated and sol- vated systems show a dual fluorescence phenomenon, consisting of a LE emission band and a red-shifted ICT band. Our calculations including the solvent effects indicate that the dual fluorescence is brought about by the change in molecular structure connected with the planarization of the twisted N-phenylphenanthridinone during the ICT reaction.

  11. Theoretical and Experimental Investigation of a 4 K Single-Stage Stirling Type Pulse Tube Cryocooler with Precooling (United States)

    Li, Z. P.; Chen, J.; Gan, Z. H.; Qiu, L. M.


    The efficiency of 4 K Stirling type pulse tube cryocoolers (SPTC) is rather low compared with that of 80 K SPTCs. Real gas effects and low specific heat capacity ratio of regenerator matrix to helium near 4 K are the main reasons that lead to the low efficiency of 4 K SPTC. A single-stage Stirling type PTC precooled by a two-stage G-M type PTC is developed to study the performance of 4 K Stirling type PTC with a focus on the performance of the regenerator working at 4 K-10 K. In order to reduce loss associated with real gas effects, relatively low average pressure was used. Gd2O2S (GOS) was used as regenerator matrix to replace HoCu2 around 4 K to decrease the regenerator loss caused by ineffective heat transfer between regenerator matrix and helium. A systematic comparison between the two types of regenerator matrix was made theoretically and experimentally including effect of frequency, average pressure and precooling temperature. Performance of the linear compressor is also presented in this paper.

  12. Dumbbell-type fullerene-steroid hybrids: a join experimental and theoretical investigation for conformational, configurational, and circular dichroism assignments. (United States)

    Ruíz, Alberto; Morera-Boado, Cercis; Almagro, Luis; Coro, Julieta; Maroto, Enrique E; Herranz, María Ángeles; Filippone, Salvatore; Molero, Dolores; Martínez-Álvarez, Roberto; Garcia de la Vega, José M; Suárez, Margarita; Martín, Nazario


    New [60]fullerene-steroid conjugates (4-6) have been synthesized by 1,3-dipolar cycloaddition and Bingel-Hirsch cyclopropanation reactions from suitably functionalized epiandrosterone and [60]fullerene. Since a new stereocenter is created in the formation of the Prato monoaduct, two different diastereomers were isolated by HPLC (4, 5) whose absolute configurations were assigned according to the highly reliable "sector rule" on fullerenes. A further reaction of the malonate-containing diastereomer 5 with a second C60 molecule has afforded dumbbell fullerene 6 in which the two fullerene units are covalently connected through an epiandrosterone moiety. The new compounds have been spectroscopically characterized and their redox potentials, determined by cyclic voltametry, reveal three reversible reduction waves for hybrids 4 and 5, whereas these signals are split in dumbbell 6. Theoretical calculations at semiempirical (AM1) and single point B3LYP/6-31G(d) levels have predicted the most stable conformations for the hybrid compounds (4-6), showing the importance of the chlorine atom on the D ring of the steroid. Furthermore, TDDFT calculations have allowed assignments of the experimentally determined circular dichroism (CD) of the [60]fullerene-steroid hybrids based on the sign and position of the Cotton effects, despite the exceptionally large systems under study.

  13. Theoretical Investigation on Excitation, Ionization and Capture in H(1s, 2s) + H(1s, 2s) Collisions

    Institute of Scientific and Technical Information of China (English)

    CHEN Lan-Fang; ZHU Xiao-Long; MA Xin-Wen; LIU Ling; HE Bin; WANG Jian-Guo; Ratko JANEV


    @@ Cross sections of electron-loss in H(1s)+ H(1s) collisions and total collisional destruction of H(2s) in H(1s) + H(2s) collisions are calculated by four-body classical-trajectory Monte Carlo (CTMC) method and compared with previous theoretical and experimental data over the energy range of 4-100 keV. For the former a good agreement is obtained within different four-body CTMC calculations, and for the incident energy Ep > 10 keV, comparison with the experimental data shows a better agreement than the results calculated by the impact parameter approx-imation. For the latter, our theory predicts the correct experimental behaviour, and the discrepancies between our results and experimental ones are less than 30%. Based on the successive comparison with experiments, the cross sections for excitation to H(2p), single- and double-ionization and H- formation in H(2s)+H(2s) collisions are calculated in the energy range of 4-100 keV for the first time, and compared with those in H(1s)+H(1s) and H(1s)+H(2s) collisions.

  14. Theoretical investigation of the magnetic exchange interactions in copper(II) oxides under chemical and physical pressures. (United States)

    Rocquefelte, Xavier; Schwarz, Karlheinz; Blaha, Peter


    It remains a challenge to understand the unconventional mechanisms that cause high-T(C) superconductivity in cuprate superconductors, high-T(C) multiferroicity in CuO, or low-dimensional magnetism in the spin-Peierls transition compounds such as CuGeO(3). A common feature of all these copper oxide compounds (containing Cu(2+) ions) is the presence of large magnetic superexchange interactions J. It is a general strategy to apply chemical and/or physical pressure in order to tune these exotic properties. Here we show theoretically, for the first time, the impact of physical pressure on J on CuO, for which we predict a strong enhancement of the low-dimensionality of the magnetic interactions and the spin-frustration at high-pressures. Such modifications are expected to strongly influence the multiferroic properties of CuO. We finally demonstrate that PBE0 hybrid DFT calculations provide reliable J values for a wide range of copper(II) oxides compounds, i.e. CuGeO(3), BaCu(2)Si(2)O(7), BaCu(2)Ge(2)O(7), and La(2)CuO(4).

  15. Synthesis, X-ray structure and theoretical investigation of 2-(2'-quinolyl)benzimidazole metal complexes

    Indian Academy of Sciences (India)



    Synthesis, characterization and DFT analysis of 2-(1H-benzo[d]imidazol-2-yl)quinoline (BQ) and its cobalt and manganese coordination compounds {Co(DMF)(BQ) Cl₂} and {Mn(DMF)(BQ) Cl₂} have been described. The ligand, 2-(1H-benzo[d]imidazol-2-yl)quinoline (BQ) crystallizes in non-centrosymmetric monoclinic crystal system with cell parameters a = 12.9280(4) Å, b = 7.9429(3) Å, c = 25.8478(9) Å, α =γ = 90◦, β = 103.005(2)◦. {Co(DMF)(BQ)Cl₂} and {Mn(DMF)(BQ)Cl₂} crystallized in triclinic space group P-1. The metal(II) environment exhibits trigonal bipyramidal coordination. These complexes show presence of N–H. . .Cl, C–H...Cl hydrogen bonds and strong intramolecular C–H...O interactions. The structure parameters were calculated and they are in good agreement with those observed experimentally. Theoretically calculated frontier molecular orbitals (HOMO–LUMO) of the complexes and their energies indicate intermolecular chargetransfer and delocalization of electron density within the molecule.

  16. Theoretical investigations into spectral and non-linear optical properties of brucine and strychnine using density functional theory. (United States)

    Islam, Nasarul; Niaz, Saba; Manzoor, Taniya; Pandith, Altaf Hussain


    The density functional theoretical (DFT) computations were performed at the B3LYP/6-311G++(d, p) level to calculate the equilibrium geometry, vibrational wave numbers, intensities, and various other molecular properties of brucine and strychnine, which were found in satisfactory agreement with the experimental data. The out-of-phase stretching modes of aromatic rings and carbonyl stretching modes in combination with CH stretching modes at stereogenic centers generate VCD signals, which are remarkably efficient configuration markers for these chiral molecular systems. NBOs analysis reveals that the large values of second order perturbation energy (47.24kcal/mol for brucine and 46.93kcal/mol for strychnine) confirms strong hyperconjugative interaction between the orbital containing the lone pair of electron of nitrogen and the neighboring CO antibonding orbital. The molecular electrostatic potential map of strychnine molecule, with no polar groups other than the lone keto group, shows less polarization, which accounts for its lower susceptibility towards electrophilic attack as compared to brucine.

  17. Theoretical investigations on the geometric and electronic structures of polyacetylene molecule under the influence of external electric field

    Directory of Open Access Journals (Sweden)


    Full Text Available The geometric and electronic structures of all-trans polyacetylene (PA molecule in neutral, cationic, and anionic states have been studied theoretically by density functional theory method at the B3LYP/6-31+G* level. The results show that both the geometric and electronic structures of the PA molecule are sensitive to the external electric field (EF. For neutral PA molecule, with the increase of EF, the carbon-carbon single bonds are shortened while the carbon-carbon double bonds are elongated. The energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (LUMO-HOMO gap decreases with the EF increasing. For cationic PA molecule, the carbon-carbon single bonds and carbon-carbon double bonds on the high potential side are elongated and shortened, respectively. While, the carboncarbon single bonds and carbon-carbon double bonds on the low potential side are shortened and elongated, respectively. Contrary to the neutral PA case, the LUMO-HOMO gap increases with the EF increasing. Contrast to the case of cationic PA, the evolution of carbon-carbon bond lengths for the anionic PA molecule under the external EF reverses. The LUMO-HOMO gap of the anionic PA molecule decreases with the increase of external EF. In addition, the spatial distributions of the HOMO and LUMO under the influence of external EF are also discussed for the PA molecule in neutral, cationic, and anionic states.

  18. Theoretical investigation of hydrogen bonding between water and platinum(II): an atom in molecule (AIM) study (United States)

    Li, Yan; Zhang, Guiqiu; Chen, Dezhan


    Recently, Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] [1] reported a hydrogen-bonding-like interaction between a water molecule and a d8 metal ion (PtII) based on neutron diffraction, and provided the first crystallographic evidence for this interaction. We studied the hydrogen bonding of the O-H ... Pt interaction theoretically using atoms in molecule (AIM) and natural bond orbital analysis (NBO) in the crystallographic geometries. The method used density functional theory (DFT) with the hybrid B3LYP function. For platinum atoms, we used the Los Alamos National Laboratory 2-Double-Zeta (LANL2DZ) basis set, and for the other atoms we used 6-311++G(d,p) basis sets. Criteria based on a topological analysis of the electron density were used in order to characterize the nature of interactions in the complexes. The main purpose of the present work is to provide an answer to the following questions: Why can a filled d orbital of square-planar d8 metal ions such as platinum(II) also act as hydrogen-bond acceptors? Can a study based on the electron charge density answer this question? A good correlation between the density at the intermolecular bond critical point and the energy interaction was found. The interaction is mainly closed-shell and there is some charge transfer in this system.

  19. Progress in theoretical, experimental, and computational investigations in turbid tissue phantoms and human teeth using laser infrared photothermal radiometry (United States)

    Mandelis, Andreas


    This paper reviews and describes the state-of-the-art in the development of frequency-domain infrared photothermal radiometry (FD-PTR) for biomedical and dental applications. The emphasis is placed on the measurement of the optical and thermal properties of tissue-like materials using FD-PTR. A rigorous three-dimensional thermal-wave formulation with three-dimensional diffuse and coherent photon-density-wave sources is presented, and is applied to data from model tissue phantoms and dental enamel samples. The combined theoretical, experimental and computational methodology shows good promise with regard to its analytical ability to measure optical properties of turbid media uniquely, as compared to PPTR, which exhibits uniqueness problems. From data sets obtained with calibrated test phantoms, the reduced optical scattering and absorption coefficients were found to be within 20% and 10%, respectively, from the independently derived values using Mie scattering theory and spectrophotometric measurements. Furthermore, the state-of-the-art and recent developments in applications of laser infrared FD-PTR to dental caries research is described, with examples and histological studies from carious dental tissue. The correlation of PTR signals with modulated dental luminescence is discussed as a very promising potential quantitative methodology for the clinical diagnosis of sub-surface incipient dental caries. The application of the turbid-medium thermal-wave model to the measurement of the optical absorption and scattering coefficients of enamel is also presented.

  20. Effect of TiO2 particles on normal and resonance Raman spectra of coumarin 343: a theoretical investigation. (United States)

    Yang, Linzhi; Wu, Wenpeng; Zhao, Yi


    It is well known that interfacial structures and charge transfer in dye-sensitized solar cells are extremely important for the enhancement of cell efficiency. Here, the normal Raman spectra (NRS) and resonance Raman spectra (RRS) of a C343-sensitized TiO2 cluster (Ti9O18) are theoretically predicted from combined electronic structure calculations and a vibrationally-resolved spectral method to reveal the relationship between interfacial geometries and excited-state dynamics. The results show that although the NRS of free C343 and the C343-TiO2 cluster correspond to the vibrational motions of C343 in a high frequency domain, their mode frequencies show obvious differences due to the interaction of the TiO2 cluster on C343, and several new Raman active fingerprint modes, such as bidentate chelating bonding modes, can be used to determine interfacial geometries. However, the resonance Raman activities of low-frequency modes are significantly enhanced and several modes from the TiO2 cluster can be observed, consistent with experimental measurements. Furthermore, the RRS from a locally excited state and a charge transfer state of C343-TiO2 are dramatically different, for instance, new Raman active modes with 1212 cm(-1), 1560 cm(-1) and 1602 cm(-1), corresponding to the motions of CH2 rocking, C=C/C-N/C=O stretching and C=O/C=C stretching, appear from the charge transfer state. The obtained information on mode-specific reorganization energies from these excited states is greatly helpful to understand and control interfacial electron transfer.

  1. Theoretical investigations of the operating characteristics of circulating pressurized fluidized bed combustors; Theoretische Untersuchungen zum Betriebsverhalten zirkulierender Druckwirbelschichtfeuerungen

    Energy Technology Data Exchange (ETDEWEB)

    Foerster, M.; Krumm, W.


    The combination of gas turbine and water-/steam cycle is a proper alternative to increase the efficiency of power plants. Coal fired power plants can be designed as reactors with pressurized coal gasification, pressurized coal dust combustion or a pressurized fluidized bed combustion to realize these plant design. Mathematical modeling and simulation are used to support the development of new power plant concepts, e.g. pressurized fluidized bed combustion. In this paper a one-dimensional model for a pressurized fluidized circulating bed combustion power plant is presented. The modeling structure allows to vary different parameters to identify the particular influence on the overall plant behavior. The model is enlarged by a more detailed balance for limestone. After describing the theoretical background of the influence of added limestone rate on the emissions of sulfurdioxide is shown. (orig.) [German] Ausgehend vom Prinzip eines Dampfkraftwerks mit atmosphaerischer Wirbelschichtfeuerung werden der Dampf- und Gasturbinenprozess bei den druckaufgeladenen Konzepten quasi parallel betrieben und die Gasturbine mit dem Rauchgas aus der Kohlenfeuerung beaufschlagt. Die wesentlichen Unterschiede zu erdgas- oder oelbefeuerten Kombianlagen sind bei den Druckwirbelschichtkonzepten, durch den in Zusammensetzung und Feuchtegehalt stark variierenden Brennstoff Kohle und durch die Auskopplung grosser Waermemengen bei der integrierten Dampferzeugung, gegeben. Der Hauptanteil der erzeugten elektrischen Leistung entfaellt auf den Dampfturbinenprozess. Druckwirbelschichtanlagen mit blasenbildender Wirbelschicht sind seit Anfang der 90er Jahre in Betrieb. Entsprechend der Entwicklung bei der atmopshaerischen Wirbelschichtfeuerung zeichnet sich als naechste Generation dieses Kraftwerkstyps die zirkulierende Druckwirbelschicht mit Heissgasfilter ab. Die mathematische Modellbildung hat sich zu einem anerkannten Werkzeug zur Unterstuetzung der Auslegung und der Untersuchung der Wirkung

  2. Theoretical investigation of active sites at the corners of Mgcl 2 crystallites in supported ziegler-natta catalysts

    KAUST Repository

    Correa, Andrea


    We present a theoretical study on possible models of catalytic active species corresponding to Ti-chloride species adsorbed at the corners of MgCl 2 crystallites. First we focused our efforts on the interaction between prototypes of three industrially relevant Lewis bases used as internal donors (1,3-diethers, alkoxysilanes and succinates) and MgCl 2 units at the corner of a MgCl 2 crystallite. Our calculations show that the energetic cost to extract MgCl 2 units at the corner of (104) edged MgCl 2 crystallites is not prohibitive, and that Lewis bases added during catalyst preparation make this process easier. After removal of one MgCl 2 unit, a short (110) stretch joining the (104) edges is formed. Adsorption of TiCl 4 on the generated vacancy originates a Ti-active species. In the second part of this manuscript, we report on the stereo- and regioselective behavior of this model of active species in the absence as well as in the presence of the three Lewis bases indicated above. Surface reconstruction due to the additional adsorption of an extra MgCl 2 layer is also considered. We show that, according to experimental data, Lewis bases coordinated in the proximity of the active Ti center confer a remarkable stereoselectivity. Moreover, surface reconstruction as well as donor coordination would improve regioselectivity by disfavoring secondary propene insertion. While still models of possible active species, our results indicate that defects, corners and surface reconstruction should be considered as possible anchoring sites for the catalytically active Ti-species. © 2012 American Chemical Society.

  3. Theoretical Investigation on the Substituent Effect of Halogen Atoms at the C8 Position of Adenine: Relative Stability, Vibrational Frequencies, and Raman Spectra of Tautomers. (United States)

    Chen, Yan-Li; Wu, De-Yin; Tian, Zhong-Qun


    We have theoretically investigated the substituent effect of adenine at the C8 position with a substituent X = H, F, Cl, and Br by using the density functional theory (DFT) at the B3LYP/6-311+G(d, p) level. The aim is to study the substituent effect of halogen atoms on the relative stability, vibrational frequencies, and solvation effect of tautomers. Our calculated results show that for substituted adenine molecules the N9H8X tautomer to be the most stable structure in gas phase at the present theoretical level. Here N9H8X denotes the hydrogen atom binds to the N9 position of imidazole ring and X denotes H, F, Cl, and Br atoms. The influence of the induced attraction of the fluorine substituent is significantly larger than chlorine and bromine ones. The halogen substituent effect has a significant influence on changes of vibrational frequencies and Raman intensities.

  4. Kinetics and thermodynamics of the reaction between the •OH radical and adenine – a theoretical investigation

    DEFF Research Database (Denmark)

    Milhøj, Birgitte Olai; Sauer, Stephan P. A.


    The accessibility of all possible reaction paths for the reaction between the nucleobase adenine and the •OH radical is investigated through quantum chemical calculations of barrier heights and rate constants at the wB97X-D/6-311++G(2df,2pd) level with Eckart tunneling corrections. First the comp...

  5. Theoretical investigations of electronic structure and magnetism in Zr{sub 2}CoSn full-Heusler compound

    Energy Technology Data Exchange (ETDEWEB)

    Birsan, A. [National Institute of Materials Physics, Atomistilor Str., No. 105 bis PO Box MG-7, 077125 Magurele (Romania); University of Bucharest, Faculty of Physics, Atomistilor Str., No. 105 PO Box MG-11, 077125 Magurele (Romania); Kuncser, V. [National Institute of Materials Physics, Atomistilor Str., No. 105 bis PO Box MG-7, 077125 Magurele (Romania)


    The half-metallic properties of a new and promising full-Heusler compound, Zr{sub 2}CoSn, are investigated by means of ab initio calculations within the Density Functional Theory framework. It was shown that the ferromagnetic ordered Hg{sub 2}CuTi-type crystal structure is energetically the most favorable for this compound. The total magnetic moment is 3 μ{sub B}/f.u. and follows a typical Slater–Pauling dependence. The half metallicity disappears if the unit cell volume is contracted by more than 5%. - Highlights: • Electronic structure and magnetic properties of Zr{sub 2}CoSn were investigated. • The calculated equilibrium lattice parameter is a=6.76 Å • The total magnetic moment of Zr{sub 2}CoSn is 3 μ{sub B}/f.u. • Full spin polarization is at the ground state.

  6. A Theoretical Investigation on the Reaction Mechanism of the C9H+ 12·Side-chain Decomposition

    Institute of Scientific and Technical Information of China (English)

    CHENG,Xueli; ZHAO,Yanyun; LI,Feng; ZHANG,Dongsheng


    n-Phenylpropane cation C9H+·12 serves as a prototype to investigate the reaction mechanisms of alkylbenzene cations.The decomposition reactions of C9H+·12 system have been studied extensively at the B3LYP/6-311 + + G**level with Gaussian 98 program package.All reaction channels were fully investigated with the vibrational mode analysis to confirm the transition states and with electron population analysis to discuss the electron redistribution,and to elucidate the reaction mechanism.The reaction mechanism shows that there is a non-barrier channel of C9H+·12→C7H+7+C2H·5,which is thermodynamically most favorable.

  7. Theoretical investigation on ratiometric two-photon fluorescent probe for Zn2+ detection based on ICT mechanism (United States)

    Huang, Shuang; Yang, Bao-Zhu; Ren, Ai-Min


    OPA (one-photon absorption), TPA (two-photon absorption) and fluorescence properties of a free ligand L upon coordination with Zn2+, and the regeneration with CN- were investigated in theory. According to our research, OPA spectra of ligand L show red-shift binding with Zn2+ while blue-shift with CN-. The fluorescence spectra and TPA wavelength are shifted in the same situation as those of OPA spectra. The value of TPA cross-section decreased at first, and then increased to 1813 GM for [L-Zn(CN)4]2-. Intramolecular charge transfer (ICT) mechanism was investigated by natural bond orbital (NBO) analysis. It demonstrates that L is hopeful to be a good ratiometric fluorescent probe for zinc ion detection in solution, and it can regenerate after CN- was introduced.

  8. Experimental and theoretical investigation of HT-S/PMR-PI composites for application to advanced aircraft engines (United States)

    Hanson, M. P.; Chamis, C. C.


    Investigations were performed in order to: (1) demonstrate that high quality angleplied laminates can be made from HT-S/PMR-PI (PMR in situ polymerization of monomeric reactants), (2) characterize the PMR-PI material and to determine the HT-S unidirectional composite properties required for composite micro and macromechanics and laminate analyses, and (3) select HT-S/PMR laminate configurations to meet the general design requirements for high-tip-speed compressor blades. The results of the investigation show that HT-S/PMR laminate configurations can be fabricated which satisfy the high-tip-speed compressor blade design requirements when operating within the temperature capability of the polyimide matrix.

  9. Theoretical investigation of pressure-induced structural transitions in americium using GGA+U and hybrid density functional theory methods

    DEFF Research Database (Denmark)

    Verma, Ashok K.; Modak, P.; Sharma, Surinder M.;


    First-principles calculations have been performed for americium (Am) metal using the generalized gradient approximation + orbital-dependent onsite Coulomb repulsion via Hubbard interaction (GGA+U) and hybrid density functional theory (HYB-DFT) methods to investigate various ground state properties...... spectrum at ambient pressure relate, for some parameter choices, well to peak positions in the calculated density of states function of Am-I....

  10. Experimental and theoretical investigation of a pyridine containing Schiff base: Hirshfeld analysis of crystal structure, interaction with biomolecules and cytotoxicity (United States)

    Chithiraikumar, S.; Neelakantan, M. A.


    A pyridine containing Schiff base (E)-2-methoxy-6-(((pyridin-2-ylmethyl)imino)methyl) phenol (L) was isolated in single crystals. The molecular structure of L was studied by FT-IR, NMR, UV-Vis techniques, single crystal XRD analysis and computationally by DFT method. L prefers enol form in the solid state. Electronic spectrum of L was recorded in different organic solvents to investigate the dependence of tautomerism on solvent types. The polar solvents facilitate the proton transfer by decreasing the activation energy needed for transition state. Potential energy curve for the intramolecular proton transfer in the ground state is generated in gas and solution phases. The 3D Hirshfeld surfaces and the associated 2D fingerprint plots were investigated. The percentages of various interactions were analyzed by fingerprint plots of Hirshfeld surface. The interaction of L with CT DNA was investigated under physiological conditions using UV-Vis spectroscopy, fluorescence quenching and molecular docking methods. Molecular docking studies reveal that binding of L to the groove of B-DNA is through hydrogen bonding and hydrophobic interactions. The in vitro cytotoxicity of L was carried out in two different human tumor cell lines, MCF 7 and MIA-Pa-Ca-2 exhibits moderate activity.

  11. Investigation of endogenous blood lipids components that contribute to matrix effects in dried blood spot samples by liquid chromatography-tandem mass spectrometry. (United States)

    Ismaiel, Omnia A; Jenkins, Rand G; Karnes, H Thomas


    Dried blood spot (DBS) sampling coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) is a rapidly developing approach in the field of biopharmaceutical analysis. DBS sampling enables analysis of small sample volumes with high sensitivity and selectivity while providing a convenient easy to store and ship format. Lipid components that may be extracted during biological sample processing may result in matrix ionization effects and can significantly affect the precision and accuracy of the results. Glycerophosphocholines (GPChos), cholesterols and triacylglycerols (TAG) are the main lipid components that contribute to matrix effects in LC-MS/MS. Various organic solvents such as methanol, acetonitrile, methyl tertiary butyl ether, ethyl ether, dichloromethane and n-hexane were investigated for elution of these lipid components from DBS samples. Methanol extracts demonstrated the highest levels of GPChos whereas ethyl ether and n-hexane extracts contained less than 1.0 % of the GPChos levels in the methanol extracts. Ethyl ether extracts contained the highest levels of cholesterols and TAG in comparison to other investigated organic solvents. Acetonitrile is recommended as an elution solvent due to low lipid recoveries. Matrix effects resulted from different extracted lipid components should be studied and assessed carefully in DBS samples.

  12. Theoretical investigation of the mechanical and thermodynamics properties of Nb{sub 3}Ga superconductor under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Wenyan, E-mail: [College of Electronics and Information Engineering, Taiyuan University of Science and Technology, Taiyuan 030024 (China); Chen, Haichuan [College of Electrical Engineering and Information Technology, Xihua University, Chengdu 610039 (China)


    The mechanical and thermodynamics properties of Nb{sub 3}Ga under pressure have been studied and analyzed using first-principles combined with quasi-harmonic Debye model. The calculated lattice parameter of the ground state is in well agreement with the experimental data. The pressure dependence of a/a{sub 0} and V/V{sub 0} are investigated, the bulk modulus B{sub 0} and its pressure derivative B{sup ′} are found to be 164.5 GPa and 3.936, respectively. The elastic constants under pressure are obtained and the polycrystalline elastic moduli of Nb{sub 3}Ga are calculated derived from the single-crystal elastic constants. The results show that Nb{sub 3}Ga is stable and behaves in a ductile manner up to 40 GPa. In addition, the elastic anisotropy, Vickers hardness as well as the melting temperature of Nb{sub 3}Ga are investigated. Finally, the pressure and temperature dependence of the thermodynamic properties are also been obtained in the ranges of 0–40 GPa and 0–1000 K through the quasi-harmonic Debye model. - Highlights: • The physical properties of Nb{sub 3}Ga were investigated. • The bulk modulus B{sub 0} and its pressure derivative B{sup ′} are found to be 164.5 GPa and 3.936. • The Nb{sub 3}Ga is stable and behaves in a ductile manner up to 40 GPa. • The temperature dependence of the thermodynamic properties is obtained. • The 3D figures of the Young's modulus for Nb{sub 3}Ga are obtained under pressure.

  13. Theoretical investigation of the broad one-photon absorption line-shape of a flexible symmetric carbazole derivative. (United States)

    Liu, Yanli; Cerezo, Javier; Santoro, Fabrizio; Rizzo, Antonio; Lin, Na; Zhao, Xian


    The one-photon absorption spectrum of a carbazole derivative has been studied by employing density functional response theory combined with a mixed quantum/classical (QC) approach to simulate the spectral shape. In a first step of our analysis we employed the vertical gradient (VG) vibronic model to investigate the role of Franck-Condon (FC) profiles of the first ten electronic excited states of the system, underlying most of the range of the experimental spectrum. We then focussed on the first six excited states covering the low-energy region of the spectrum, and investigated the effect of inter-state electronic couplings on the spectral shapes within Herzberg-Teller (HT) theory. Furthermore, in order to introduce the broadening effects due to the two inter-ring torsions, we employed a QC approach, adopting VG vibronic models for high-frequency modes and computing the contribution of the torsions to the spectrum from the distribution of the excitation energies along a two-dimensional relaxed potential energy. Finally, we estimated the solvent inhomogeneous broadening by computing the solvent reorganization energy using a polarizable continuum model. Our calculations allow us to obtain a non-phenomenological description of the low-energy part of the spectrum in semi-quantitative agreement with experiment and to dissect the relative importance of solvent, torsional flexibility, FC vibronic progressions, and inter-state couplings in determining its broad spectral shapes and the modulation of its intensity. Our analysis also clearly highlights that the investigated carbazole represents a big challenge for available methodologies due to the existence of many close-lying excited electronic states coupled by internal low-frequency and high-frequency motions and by solvent fluctuations. The study of their impact on the spectra at the HT level is only approximate and more refined treatments would require a fully quantum-dynamical calculation on the manifold of the coupled

  14. Theoretical Investigation of Influence of Mechanical Stress on Magnetic Properties of Ferromagnetic/Antiferromagnetic Bilayers Deposited on Flexible Substrates

    Institute of Scientific and Technical Information of China (English)

    Yu-Hao Bai; Xia Wang; Lin-Ping Mu; Xiao-Hong Xu


    Effect of mechanical stress on magnetic properties of an exchange-biased ferromagnetic/antiferromagnetic bilayer deposited on a flexible substrate is investigated.The hysteresis loops with different magnitudes and orientations of the stress can be classified into three types.The corresponding physical conditions for each type of the loop are deduced based on the principle of minimal energy.The equation of the critical stress is derived,which can judge whether the loops show hysteresis or not.Numerical calculations suggest that except for the magnitude of the mechanical stress,the relative orientation of the stress is also an important factor to tune the exchange bias effect.

  15. Experimental and theoretical investigation of electro-optic and all-optical implementations of wavelength converting 2R-regenerators

    DEFF Research Database (Denmark)

    Wolfson, David; Mikkelsen, Benny; Danielsen, Søren Lykke


    We investigate and compare the regenerative capability of electro-optic wavelength converters based on electrically controlled external Mach-Zehnder (MZ) modulators and all-optical wavelength converters based on all-optically controlled external MZ modulators. The latter incorporates semiconductor...... optical amplifiers (SOAs) as optically controlled phase shifters. Experiments demonstrate a 5-6 dB noise suppression capability for both the electro-optic and the all-optical implementation of the wavelength-converting regenerators. The performance can be further improved by cascading two converters...

  16. Structural and theoretical investigations of short hydrogen bonds: neutron diffraction and plane-wave DFT calculations of urea phosphoric acid (United States)

    Wilson, Chick C.; Morrison, Carole A.


    Low temperature neutron diffraction and high level computational methods have been applied to investigate the short hydrogen bond in urea-phosphoric acid. It is found that isolated molecule calculations predict a `normal' O-H⋯O hydrogen bond, in strong disagreement with the very short, 3 c-4 e hydrogen bond found from the neutron diffraction. Extending these calculations into a periodic environment using plane-wave DFT methods give much improved agreement with experiment, with a much shorter, stronger hydrogen bond, and significant elongation of the O-H `covalent' bond.

  17. Inhibition of carbon steel corrosion in CO{sub 2}-saturated brine using some newly surfactants based on palm oil: Experimental and theoretical investigations

    Energy Technology Data Exchange (ETDEWEB)

    Abd El-Lateef, Hany M., E-mail: [Chemistry Department, Faculty of Science, Sohag University, Sohag (Egypt); Abbasov, V.M.; Aliyeva, L.I.; Qasimov, E.E.; Ismayilov, I.T. [Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, AZ1025 Baku (Azerbaijan)


    New surfactants from the type of fatty acids derivatives were synthesized based on palm oil and their inhibitive action against the corrosion of carbon steel in CO{sub 2}-saturated 1% NaCl solution were investigated at 50 °C. The detailed study of surfactants as corrosion inhibitors is given using polarization curves and electrochemical impedance spectroscopy methods. The inhibition efficiencies obtained from the two employed methods are nearly closed. Results show that, the investigated surfactants are good inhibitors and its inhibition efficiency reaches to 98.95% at 100 ppm for inhibitor V. The high inhibition efficiencies were attributed to the simple blocking effect by adsorption of inhibitor molecules on the steel surface. The surface activity of the synthesized surfactant solutions was determined using surface tension measurements at 25 °C. Adsorption of the inhibitors on the carbon steel surface was found to obey Langmuir's adsorption isotherm and chemisorption. The correlation between the inhibition efficiencies of the studied surfactants and their molecular structures has been investigated using quantum chemical calculations. The obtained theoretical results have been supported our experimental data. - Graphical abstract: To investigate the relationship between molecular structures of the studied surfactants and their inhibition effect; Quantum chemical molecular calculations were performed. The following quantum chemical indices such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), energy gap ΔE = E{sub HOMO} − E{sub LUMO}, and dipole moment (μ) were considered. The relation between these parameters and the inhibition efficiencies was explained. The obtained theoretical results have been supported our experimental data. - Highlights: • Effect of surfactants on carbon steel corrosion in CO{sub 2}-saturted brine was investigated. • The high inhibition efficiency attributed to the adherent adsorption

  18. Impact of the column hardware volume on resolution in very high pressure liquid chromatography non-invasive investigations. (United States)

    Gritti, Fabrice; McDonald, Thomas; Gilar, Martin


    The impact of the column hardware volume (≃ 1.7 μL) on the optimum reduced plate heights of a series of short 2.1 mm × 50 mm columns (hold-up volume ≃ 80-90 μL) packed with 1.8 μm HSS-T3, 1.7 μm BEH-C18, 1.7 μm CSH-C18, 1.6 μm CORTECS-C18+, and 1.7 μm BEH-C4 particles was investigated. A rapid and non-invasive method based on the reduction of the system dispersion (to only 0.15 μL(2)) of an I-class Acquity system and on the corrected plate heights (for system dispersion) of five weakly retained n-alkanophenones in RPLC was proposed. Evidence for sample dispersion through the column hardware volume was also revealed from the experimental plot of the peak capacities for smooth linear gradients versus the corrected efficiency of a weakly retained alkanophenone (isocratic runs). The plot is built for a constant gradient steepness irrespective of the applied flow rates (0.01-0.30 mL/min) and column lengths (2, 3, 5, and 10 cm). The volume variance caused by column endfittings and frits was estimated in between 0.1 and 0.7 μL(2) depending on the applied flow rate. After correction for system and hardware dispersion, the minimum reduced plate heights of short (5 cm) and narrow-bore (2.1mm i.d.) beds packed with sub-2 μm fully and superficially porous particles were found close to 1.5 and 0.7, respectively, instead of the classical h values of 2.0 and 1.4 for the whole column assembly.

  19. Experimental and theoretical investigation of the effect of SiO2 content in gate dielectrics on work function shift induced by nanoscale capping layers

    KAUST Repository

    Caraveo-Frescas, J. A.


    The impact of SiO2 content in ultrathin gate dielectrics on the magnitude of the effective work function (EWF) shift induced by nanoscale capping layers has been investigated experimentally and theoretically. The magnitude of the effective work function shift for four different capping layers (AlN, Al2O3, La2O3, and Gd2O3) is measured as a function of SiO2 content in the gate dielectric. A nearly linear increase of this shift with SiO2 content is observed for all capping layers. The origin of this dependence is explained using density functional theory simulations.

  20. Computational Design, Theoretical and Experimental Investigation of Carbon Nanotube (CNT) - Metal Oxide/Metal Hydride Composite - A Practicable Hydrogen Storage Medium for Fuel Cell - 3 (United States)


    18 2 Theoretical Investigation First Principles Study of Hydrogen Storage in SWCNT Functionalized with metal complexes ( MgH2 , TiO2 & SnO2...10,10) armchair single walled carbon nanotube (SWCNT) functionalized with some metal complexes (Magnesium hydride ( MgH2 ), Titanium dioxide (TiO2...points scheme. As a beginning, single molecule of MgH2 (TiO2, SnO2) is attached to the CNT. The molecules are attached at a large distance in the outer

  1. A theoretical investigation of Ferromagnetic Resonance Linewidth and damping constants in coupled trilayer and spin valve systems

    Energy Technology Data Exchange (ETDEWEB)

    Layadi, A. [LESIMS, Departement de Physique, Université Ferhat Abbas, Sétif 19000 (Algeria)


    The ferromagnetic resonance intrinsic field linewidth ΔH is investigated for a multilayer system such as a coupled trilayer and a spin valve structure. The magnetic coupling between two ferromagnetic layers separated by a nonmagnetic interlayer will be described by the bilinear J{sub 1} and biquadratic J{sub 2} coupling parameters. The interaction at the interface of the first ferromagnetic layer with the antiferromagnetic one is account for by the exchange anisotropy field, H{sub E}. A general formula is derived for the intrinsic linewidth ΔH. The explicit dependence of ΔH with H{sub E}, J{sub 1} and J{sub 2} will be highlighted. Analytical expressions for each mode field linewidth are found in special cases. Equivalent damping constants will be discussed.

  2. Theoretical Investigation on the Electron and Energy Transfer between Peripheral Carrier Transport Groups and Central Chromophores in Electroluminescent Materials

    Institute of Scientific and Technical Information of China (English)

    潘玉钰; 刘丹丹; 许海; 刘晓冬; 孙冠楠; 杨兵; 马於光


    The molecular materials with structures of luminescent core and peripheral carrier groups (e.g. carbazoles), have exhibited high-performance in organic light-emitting diodes (OLEDs). Present work is to understand the basic process of electronic and energy exchange between the peripheral functional groups and the central core through quantum chemical analysis. As an example, 4,7-bis(9,9-bis(6-(9H-carbazol-9-yl)hexyl)-9H-fluoren-2-yl)benzo[c]- [1,2,5]thiadiazole (TCBzC) is investigated in regards to optoelectronic properties using density functional theory (DFT). The results suggest that the forbidden transition from peripheral carbazole to the central chromophore core makes for separated electrical and optical properties, and high performance electroluminescence (EL) is mainly at- tributed to the energy-transfer from carbazoles to the fluorene derivative core.

  3. Synthesis, structural characterization, antimicrobial activities and theoretical investigations of some 4-(4-aminophenylsulfonyl) phenylimino) methyl)-4-(aryldiazenyl) phenol (United States)

    Ghasemian, Motaleb; Kakanejadifard, Ali; Karami, Tahereh


    The azo-azomethine dyes with a different substitution have been designed from the reaction of 4,4‧-diaminodiphenyl sulfone with 2-hydroxy-5-(aryldiazenyl)benzaldehyde. The compounds have been characterized by elemental analysis, Mass, IR, UV-Vis, TGA-DTA and NMR spectroscopy. The solvatochromism behaviors, effects of substitution and pH on the electronic absorption spectra of dyes were evaluated. The in vitro antimicrobial activities were also screened for their potential for antibiotic activities by broth micro dilution method. Also, the optimum molecular geometries, molecular electrostatic potential (MEP), nucleus-independent chemical shift (NICS) and frontier molecular orbitals (FMO), vibrational spectra (IR) and electronic absorption (UV-Vis) spectra of the title compounds have been investigated with the help of DFT and TDDFT methods with 6-311 ++G(d,p) basis sets and PCM calculations. The results of the calculations show excellent agreement with the experimental value.

  4. Investigation of thermally-induced phase mismatching in continuous-wave second harmonic generation: a theoretical model. (United States)

    Sabaeian, Mohammad; Mousave, Laleh; Nadgaran, Hamid


    A fraction of the fundamental beam energy deposited into nonlinear crystals to generate second harmonic waves (SHW) causes a temperature gradient within the crystal. This temperature inhomogeneity can alter the refractive index of the medium leading to a well-known effect called thermal dispersion. Therefore, the generated SHW suffers from thermal lensing and a longitudinal thermal phase mismatching. In this work by coupling the heat equation with second harmonic generation (SHG) formalism applied to type-II configuration along with walk-off effect, we investigate the continuous wave (CW) SHW beam profile and conversion efficiency when a non-linear KTP crystal is under induced thermal load. We have demonstrated for average and high powers, the thermal de-phasing lead to considerable reduction in SHG compared to an ideal case in which induced heat is neglected.

  5. Theoretical investigations of the optical and EPR spectra for trivalent cerium and ytterbium ions in orthorhombic YF3 crystal (United States)

    Liu, Hong-Gang; Zheng, Wen-Chen


    The optical spectra and electron paramagnetic resonance (EPR) parameters (g factors and hyperfine structure constants A) for trivalent cerium and ytterbium ions in YF3 crystal with orthorhombic structure are investigated together by the complete diagonalization (of energy matrix) method (CDM). The obtained results are in reasonable agreement with the experimental ones. More importantly, two magnetically nonequivalent centers in YF3 crystal observed in EPR experiments are confirmed and ascribed to their specific positions in a unit cell by our calculations based on superposition model (SPM) analysis. Such identification of local sites with different magnetic properties would help us to understand not only the EPR spectra and magnetic susceptibility of other lanthanide ions doped in crystals with the same structure as YF3 but also the energy transfer scheme between two lanthanide ions occupying such two sites. All results are discussed carefully.

  6. Theoretical investigation of the electronic structure and quantum transport in the graphene-C(111) diamond surface system. (United States)

    Selli, Daniele; Baburin, Igor; Leoni, Stefano; Zhu, Zhen; Tománek, David; Seifert, Gotthard


    We investigate the interaction of a graphene monolayer with the C(111) diamond surface using ab initio density functional theory. To accommodate the lattice mismatch between graphene and diamond, the overlayer deforms into a wavy structure that binds strongly to the diamond substrate. The detached ridges of the wavy graphene overlayer behave electronically as free-standing polyacetylene chains with delocalized π electrons, separated by regions containing only sp(3) carbon atoms covalently bonded to the (111) diamond surface. We performed quantum transport calculations for different geometries of the system to study how the buckling of the graphene layer and the associated bonding to the diamond substrate affect the transport properties. The system displays high carrier mobility along the ridges and a wide transport gap in the direction normal to the ridges. These intriguing, strongly anisotropic transport properties qualify the hybrid graphene-diamond system as a viable candidate for electronic nanodevices.

  7. Theoretical and experimental investigations of flexural wave propagation in periodic grid structures designed with the idea of phononic crystals

    Institute of Scientific and Technical Information of China (English)

    Wen Ji-Hong; Yu Dian-Long; Liu Jing-Wen; Xiao Yong; Wen Xi-Sen


    The propagation characteristics of fiexural waves in periodic grid structures designed with the idea of phononic crystals are investigated by combining the Bloch theorem with the finite element method. This combined analysis yields phase constant surfaces, which predict the location and the extension of band gaps, as well as the directions and the regions of wave propagation at assigned frequencies. The predictions are validated by computation and experimental analysis of the harmonic responses of a finite structure with 11 × 11 unit cells. The fiexural wave is localized at the point of excitation in band gaps, while the directional behaviour occurs at particular frequencies in pass bands. These studies provide guidelines to designing periodic structures for vibration attenuation.

  8. Theoretical investigation of band-gap and mode characteristics of anti-resonance guiding photonic crystal fibres

    Institute of Scientific and Technical Information of China (English)

    Yuan Jin-Hui; Sang Xin-Zhu; Yu Chong-Xiu; Xin Xiang-Jun; Zhang Jin-Long; Zhou Gui-Yao; Li Shu-Guang; Hou Lan-Tian


    With the full-vector plane-wave method (FVPWM) and the full-vector beam propagation method (FVBPM), the dependences of the band-gap and mode characteristics on material index and cladding structure parameter in anti-resonance guiding photonic crystal fibres (ARGPCFs) are sufficiently analysed. An ARGPCF operating in the near-infrared wavelength is shown. The influences of the high index cylinders, glass interstitial apexes and silica structure on the characteristics of band-gaps and modes are deeply investigated. The equivalent planar waveguide theory is used for analysing such an ARGPCF filled by the isotropic materials, and the resonance and the anti-resonance characteristics can be well predicted.

  9. Experimental and Theoretical Investigation of Wave Forces on A Partially-Perforated Caisson Breakwater with A Rock-Filled Core

    Institute of Scientific and Technical Information of China (English)

    LIU Yong; LI Yu-cheng; TENG Bin; JIANG Jun-jie


    The total horizontal and vertical forces acting on a partially-perforated caisson breakwater and their phase difference are investigated in this study. The perforated breakwater sits on the rubble filled foundation, and has a rock-filled core. An analytical solution is developed based on the eigenfunction expansion and matching method to solve the wave field around the breakwater. The finite element method is used for simulating the wave-induced flow in the rubble-filled foundation. Experiments are also conducted to study the wave forces on the perforated caissons. Numerical predictions of the present model are compared with experimental results. The phase differences between the total horizontal and vertical forces are particularly analyzed by means of experimental and numerical results. The major factors that affect the wave forces are examined.

  10. Theoretical investigation of incomplete ionization of dopants in uniform and ion-implanted 4H-SiC MESFETs

    Institute of Scientific and Technical Information of China (English)

    王守国; 张义门; 张玉明


    The effects of incomplete ionization ofnitrogen in 4H-SiC have been investigated. Poisson's equation is numerically analysed by considering the effects of Poole-Frenkel, and the effects of the potential on Nd+ (the concentration of ionized donors) and n (the concentration of electrons). The pinch-off voltages of the uniform and the ion-implanted channels of 4H-SiC metal-semiconductor field-effect transistors (MESFETs) and the capacitance of the gate are given at different temperatures. Both the Poole-Frenkel effect and the potential have influence on the pinch-off voltage VP of 4H-SiC MESFETs. Although the C-V characteristics of the ion-implanted and the uniform channel of 4H-SiC MESFETs have a clear distinction, the effects of incomplete ionization on the C-V characteristics are not significant.

  11. The hyperbolic effect of density and strength of inter beta-cell coupling on islet bursting: a theoretical investigation

    Directory of Open Access Journals (Sweden)

    Wang Xujing


    Full Text Available Abstract Background Insulin, the principal regulating hormone of blood glucose, is released through the bursting of the pancreatic islets. Increasing evidence indicates the importance of islet morphostructure in its function, and the need of a quantitative investigation. Recently we have studied this problem from the perspective of islet bursting of insulin, utilizing a new 3D hexagonal closest packing (HCP model of islet structure that we have developed. Quantitative non-linear dependence of islet function on its structure was found. In this study, we further investigate two key structural measures: the number of neighboring cells that each β-cell is coupled to, nc, and the coupling strength, gc. Results β-cell clusters of different sizes with number of β-cells nβ ranging from 1–343, nc from 0–12, and gc from 0–1000 pS, were simulated. Three functional measures of islet bursting characteristics – fraction of bursting β-cells fb, synchronization index λ, and bursting period Tb, were quantified. The results revealed a hyperbolic dependence on the combined effect of nc and gc. From this we propose to define a dimensionless cluster coupling index or CCI, as a composite measure for islet morphostructural integrity. We show that the robustness of islet oscillatory bursting depends on CCI, with all three functional measures fb, λ and Tb increasing monotonically with CCI when it is small, and plateau around CCI = 1. Conclusion CCI is a good islet function predictor. It has the potential of linking islet structure and function, and providing insight to identify therapeutic targets for the preservation and restoration of islet β-cell mass and function.

  12. Marco teórico de una investig ación social en barrios populares de Bogotá D. C. - Theoretical frame for a social investigation in slums of Bogotá D.C.

    Directory of Open Access Journals (Sweden)

    MOLNÁR, Gábor


    Full Text Available This paper originally is the theoretical introduction of the author’s M.A. degree investigation, presented at the University Javeriana with the title. El proceso de desarrollo comunitario a partir de la experiencia de la Corporación Casa Estudio en el barrio Granjas de San Pablo”. This investigation took place in „Granjas de San Pablo”, a slum of South of Bogotá D.C. (Colombia, Latin America during several years in the turn of the 20-21th centuries (between 1997–2000. The theoretical introduction gives us an overview of several social conceptions of authors and investigators who are reflecting especially on the social fragmentation of our societies all over the so called „Western World” and Latin America. The purpose of this brief introduction is to give a theoretical frame for some of the dynamics inside and outside of our societies and communities (for instance, effects of the globalization and integration, the importance of personal experiences, effects of new interpretations of the Latin American culture etc..


    Energy Technology Data Exchange (ETDEWEB)

    Radisav D. Vidic


    The first part of this study evaluated the application of a versatile optical technique to study the adsorption and desorption of model adsorbates representative of volatile polar (acetone) and non-polar (propane) organic compounds on a model carbonaceous surface under ultra high vacuum (UHV) conditions. The results showed the strong correlation between optical differential reflectance (ODR) and adsorbate coverage determined by temperature programmed desorption (TPD). ODR technique was proved to be a powerful tool to investigate surface adsorption and desorption from UHV to high pressure conditions. The effects of chemical functionality and surface morphology on the adsorption/desorption behavior of acetone, propane and mercury were investigated for two model carbonaceous surfaces, namely air-cleaved highly oriented pyrolytic graphite (HOPG) and plasma-oxidized HOPG. They can be removed by thermal treatment (> 500 K). The presence of these groups almost completely suppresses propane adsorption at 90K and removal of these groups leads to dramatic increase in adsorption capacity. The amount of acetone adsorbed is independent of surface heat treatment and depends only on total exposure. The effects of morphological heterogeneity is evident for plasma-oxidized HOPG as this substrate provides greater surface area, as well as higher energy binding sites. Mercury adsorption at 100 K on HOPG surfaces with and without chemical functionalities and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from HOPG surface enhances mercury physisorption. Plasma oxidation of HOPG provides additional surface area for mercury adsorption. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms, physisorption below 348 K and chemisorption above 348 K. No significant impact of oxygen functionalities was observed in the chemisorption region. The key findings of this study

  14. Microencapsulation of herbicide MCPA with native β-cyclodextrin and its methyl and hydroxypropyl derivatives: An experimental and theoretical investigation (United States)

    Garrido, Jorge; Cagide, Fernando; Melle-Franco, Manuel; Borges, Fernanda; Garrido, E. Manuela


    When a pesticide is released into the environment, most of it is lost before it reaches its target. An effective way to reduce environmental losses of pesticides is by using controlled release technology. Microencapsulation becomes a promising technique for the production of controlled release agricultural formulations. In this work, the microencapsulation of chlorophenoxy herbicide MCPA with native β-cyclodextrin and its methyl and hydroxypropyl derivatives was investigated. The phase solubility study showed that both native and β-CD derivatives increased the water solubility of the herbicide and inclusion complexes are formed in a stoichiometric ratio of 1:1. The stability constants describing the extent of formation of the complexes have been determined by phase solubility studies. 1H NMR experiments were also accomplished for the prepared solid systems and the data gathered confirm the formation of the inclusion complexes. 1H NMR data obtained for the MCPA/CDs complexes disclosed noticeable proton shift displacements for OCH2 group and H6 aromatic proton of MCPA provided clear evidence of inclusion complexation process, suggesting that the phenyl moiety of the herbicide was included in the hydrophobic cavity of CDs. Free energy molecular mechanics calculations confirm all these findings.

  15. Theoretical Investigation on the Electronic and Optical Properties of Poly(fluorenevinylene Derivatives as Light-Emitting Materials

    Directory of Open Access Journals (Sweden)

    Thanisorn Yakhanthip


    Full Text Available Density functional theory (DFT and time-dependent DFT (TDDFT were employed to study ground-state properties, HOMO-LUMO gaps (ΔH-L, excitation energies (Eg, ionization potentials (IPs, and electron affinities (EA for PFV-alt-PDONV and PFV-alt-PDIH-PPV having different alternating groups. Excited-state properties were investigated using configuration interaction singles (CISs while fluorescence energies were calculated using TDDFT. The results show that PFV-alt-PDONV exhibits blue-shifted energies for both HOMO-LUMO gaps (ΔH-L and excitation energies (Eg compared with PFV-alt-PDIH-PPV. The predicted IP and EA clearly indicate that PFV-alt-PDIH-PPV has both easier hole creation and electron injection than that of PFV-alt-PDONV. The maximal absorption wavelengths of all polymers are strongly assigned to π→π∗ transition. The predicted radiative lifetimes of PFV-alt-PDONV and PFV-alt-PDIH-PPV for B3LYP/6-31G(d are 0.36 and 0.61 ns, respectively, indicating that PFV-alt-PDIH-PPV should have a better performance for long-time emission than that of PFV-alt-PDONV.

  16. Theoretical investigation on the chemistry of entrapment of the elusive aminoborane (H2 N=BH2 ) molecule. (United States)

    Malakar, Tanmay; Bhunya, Sourav; Paul, Ankan


    Aminoborane (H2 N=BH2 ) is an elusive entity and is thought to be produced during dehydropolymerization of ammonia borane, a molecule of prime interest in the field of chemical hydrogen storage. The entrapment of H2 N=BH2 through hydroboration of exogenous cyclohexene has emerged as a routine technique to infer if free H2 N=BH2 is produced or not during metal-catalyzed ammonia borane dehydrogenation reactions. But to date, the underlying mechanism of this trapping reaction remains unexplored. Herein, by using DFT calculations, we have investigated the mechanism of trapping of H2 N=BH2 by cyclohexene. Contrary to conventional wisdom, our study revealed that the trapping of H2 N=BH2 does not occur through direct hydroboration of H2 N=BH2 on the double bond of cyclohexene. We found that autocatalysis by H2 N=BH2 is crucial for the entrapment of another H2 N=BH2 molecule by cyclohexene. Additionally, nucleophilic assistance from the solvent is also implicated for the entrapment reaction carried out in nucleophilic solvents. In THF, the rate-determining barrier for formation of the trapping product was predicted to be 16.7 kcal mol(-1) at M06 L(CPCM) level of theory.

  17. Theoretical investigation of potential energy surface and bound states for the van der Waals complex Ar–BrCl dimer

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Rui [School of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou (China); Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan (China); Li, Song, E-mail: [School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou (China); Chen, Shan-Jun; Chen, Yan [School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou (China); Zheng, Li-Min [Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan (China)


    Highlights: • A two-dimensional potential for Ar–BrCl is constructed at the CCSD(T) level. • The PES is characterized by three minima and two saddle points between them. • Bound state calculations were carried out for the complex. - Abstract: The intermolecular potential energy surface (PES) of the ground electronic state for the Ar–BrCl dimer is constructed at the CCSD(T) level with the aug-cc-pVQZ basis set and mid-bond functions. The PES is characterized by three minima and two saddle points. The global minimum corresponding to a collinear Ar–BrCl configuration, which has been observed experimentally, is located at R = 4.10 Å and θ = 2.5° with a well depth of −285.207 cm{sup −1}. A nearly T-shaped structure and an anti-linear Ar–ClBr geometry is also predicted. The bound state calculations are preformed to study intermolecular vibrational modes, rotational levels and average structures for the complex. Our transition frequencies, spectroscopic constants and average structures for all isotopomers of the collinear isomer agree well with experimental data. We have also provided pure rotational transitional frequencies for both nearly T-shaped and anti-linear isomers. These results are significant for further experimental investigations of the Ar–BrCl dimer.

  18. Theoretical Investigation on Single-Wall Carbon Nanotubes Doped with Nitrogen, Pyridine-Like Nitrogen Defects, and Transition Metal Atoms

    Directory of Open Access Journals (Sweden)

    Michael Mananghaya


    Full Text Available This study addresses the inherent difficulty in synthesizing single-walled carbon nanotubes (SWCNTs with uniform chirality and well-defined electronic properties through the introduction of dopants, topological defects, and intercalation of metals. Depending on the desired application, one can modify the electronic and magnetic properties of SWCNTs through an appropriate introduction of imperfections. This scheme broadens the application areas of SWCNTs. Under this motivation, we present our ongoing investigations of the following models: (i (10, 0 and (5, 5 SWCNT doped with nitrogen (CNxNT, (ii (10, 0 and (5, 5 SWCNT with pyridine-like defects (3NV-CNxNT, (iii (10, 0 SWCNT with porphyrine-like defects (4ND-CNxNT. Models (ii and (iii were chemically functionalized with 14 transition metals (TMs: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Pt and Au. Using the spin-unrestricted density functional theory (DFT, stable configurations, deformations, formation and binding energies, the effects of the doping concentration of nitrogen, pyridine-like and porphyrine-like defects on the electronic properties were all examined. Results reveal that the electronic properties of SWCNTs show strong dependence on the concentration and configuration of nitrogen impurities, its defects, and the TMs adsorbed.

  19. Theoretical investigation of the substituent effects on the electronic and optical properties of 6-substituted coumarin derivatives (United States)

    Bai, Yihui; Zhang, Fang; Ying, Jin; Wu, Yingzi


    The electronic structures, absorption and emission spectra of selected 6-substituted coumarins were investigated and compared with unsubstituted coumarin by using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods with Gaussian 09 software package. Results revealed that the presented absorption and emission spectra were affected by the substituent groups apparently. The maximum absorption wavelength of a coumarin molecule can be shifted to a longer one by introducing a large conjugated substituent, an electron donating group or a group which can form a rigid structure with the parent moiety at 6-position. The lowest energy emission of a 6-substituted coumarin can be greatly red-shifted by modifying the substituent to one which can be strongly conjugated with the phenyl ring. A group which has a strongly electron-withdrawing effect may cause a large excitation intensity and a short wavelength in emission. Most selected molecules are predicted to give the lowest-energy emissions in the purple or blue light region, which are supposed to be selected and modified as purple or blue luminescent materials. 6-nitrocoumarin is predicted as an invisible fluorescent material. 6,7-benzocoumarin, which forms a rigid conjugated ring with the parent moiety, is expected to be modified as a green luminescent material. Many of these 6-substituted coumarins are expected to be potential candidates as large Stokes shift dyes for multicolor labeling and fluorescence-activated cell sorting (FACS), especially those molecules, which bear sbnd CONH2, sbnd CN, and sbnd CH3 respectively.

  20. Experimental and theoretical investigation on corrosion inhibition of AA5052 aluminium alloy by L-cysteine in alkaline solution

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dapeng; Gao, Lixin [School of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090 (China); Zhang, Daquan, E-mail: [School of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090 (China); Yang, Dong [School of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090 (China); Wang, Hongxia; Lin, Tong [Institute for Frontier Materials, Deakin University, Geelong, VIC 3216 (Australia)


    The corrosion inhibition of L-cysteine on AA5052 aluminium alloy in 4 mol/L NaOH solution was investigated by hydrogen gas evolution experiment, polarisation curve, galvanostatic discharge, electrochemical impedance spectroscopy measurements and quantum chemical calculations. The adsorption of L-cysteine on aluminium alloy surface obeyed the amended Langmuir's adsorption isotherm. The polarisation curves indicated that L-cysteine acted as a cathodic inhibitor to inhibit cathodic reaction. The inhibition mechanism was dominated by the geometric covering effect. The galvanostatic discharge shows that the additives restrain the hydrogen evolution and increase the anodic utilization rate. Quantum chemical calculations indicated that L-cysteine molecules mainly interacted with on the carboxyl groups on the aluminium alloy surface. A strong hybridization occurred between the s-orbital and p-orbital of reactive sites in the L-cysteine molecule and the sp-orbital of Aluminium. - Highlights: • L-cysteine was used as corrosion inhibitor for Al alloy in alkaline solution. • Adsorption of L-cysteine on Al alloy surface obeyed the amended Langmuir's isotherm. • L-cysteine molecules interacted with the carboxyl groups on the Al alloy surface. • A strong orbital hybridization occurred between the reactive sites in L-cysteine and Al.

  1. Experimental and theoretical investigation of the charge-separation energies of hydrated zinc(II): redefinition of the critical size. (United States)

    Cooper, Theresa E; Armentrout, P B


    In the preceding article, the hydration energies of Zn(2+)(H(2)O)(n) complexes, where n = 6-10, were measured using threshold collision-induced dissociation (CID) in a guided ion beam tandem mass spectrometer (GIBMS) coupled with an electrospray ionization (ESI) source. The present investigation explores the charge-separation processes observed, Zn(2+)(H(2)O)(n) --> ZnOH(+)(H(2)O)(m) + H(+)(H(2)O)(n-m-1), and the competition between this process and the loss of water. Our results demonstrate that charge-separation processes occur at variable complex sizes of n = 6, 7, and 8, prompting a redefinition of the critical size for charge separation. Experimental kinetic energy-dependent cross sections are analyzed to yield 0 K threshold energies for the charge-separation products and the effects of competition with this channel on the energies for losing one and two water ligands after accounting for multiple collisions, kinetic shifts, and energy distributions. A complete reaction coordinate is calculated for the n = 7 complex dissociating into ZnOH(+)(H(2)O)(3) + H(+)(H(2)O)(3). Calculated rate-limiting transition states for n = 6-8 are also compared to experimental threshold measurements for the charge-separation processes.

  2. Theoretical investigation of the first-shell mechanism of acetylene hydration catalyzed by a biomimetic tungsten complex. (United States)

    Liu, Yan-Fang; Liao, Rong-Zhen; Ding, Wan-Jian; Yu, Jian-Guo; Liu, Ruo-Zhuang


    The reaction mechanism of the hydration of acetylene to acetaldehyde catalyzed by [W(IV)O(mnt)(2)](2-) (where mnt(2-) is 1,2-dicyanoethylenedithiolate) is studied using density functional theory. Both the uncatalyzed and the catalyzed reaction are considered to find out the origin of the catalysis. Three different models are investigated, in which an aquo, a hydroxo, or an oxo coordinates to the tungsten center. A first-shell mechanism is suggested, similarly to recent calculations on tungsten-dependent acetylene hydratase. The acetylene substrate first coordinates to the tungsten center in an η(2) fashion. Then, the tungsten-bound hydroxide activates a water molecule to perform a nucleophilic attack on the acetylene, resulting in the formation of a vinyl anion and a tungsten-bound water molecule. This is followed by proton transfer from the tungsten-bound water molecule to the newly formed vinyl anion intermediate. Tungsten is directly involved in the reaction by binding and activating acetylene and providing electrostatic stabilization to the transition states and intermediates. Three other mechanisms are also considered, but the associated energetic barriers were found to be very high, ruling out those possibilities.

  3. A theoretical investigation of the effect of proliferation and adhesion on monoclonal conversion in the colonic crypt

    KAUST Repository

    Mirams, Gary R.


    The surface epithelium lining the intestinal tract renews itself rapidly by a coordinated programme of cell proliferation, migration and differentiation events that is initiated in the crypts of Lieberkühn. It is generally believed that colorectal cancer arises due to mutations that disrupt the normal cellular dynamics of the crypts. Using a spatially structured cell-based model of a colonic crypt, we investigate the likelihood that the progeny of a mutated cell will dominate, or be sloughed out of, a crypt. Our approach is to perform multiple simulations, varying the spatial location of the initial mutation, and the proliferative and adhesive properties of the mutant cells, to obtain statistical distributions for the probability of their domination. Our simulations lead us to make a number of predictions. The process of monoclonal conversion always occurs, and does not require that the cell which initially gave rise to the population remains in the crypt. Mutations occurring more than one to two cells from the base of the crypt are unlikely to become the dominant clone. The probability of a mutant clone persisting in the crypt is sensitive to dysregulation of adhesion. By comparing simulation results with those from a simple one-dimensional stochastic model of population dynamics at the base of the crypt, we infer that this sensitivity is due to direct competition between wild-type and mutant cells at the base of the crypt. We also predict that increases in the extent of the spatial domain in which the mutant cells proliferate can give rise to counter-intuitive, non-linear changes to the probability of their fixation, due to effects that cannot be captured in simpler models. © 2012 Elsevier Ltd.

  4. Comparison of human skin opto-thermal response to near-infrared and visible laser irradiations: a theoretical investigation

    Energy Technology Data Exchange (ETDEWEB)

    Dai Tianhong [Department of Bioengineering, Rice University, Houston, TX 77251 (United States); Pikkula, Brian M [Department of Bioengineering, Rice University, Houston, TX 77251 (United States); Wang, Lihong V [Department of Biomedical Engineering, Texas A and M University, College Station, TX 77843 (United States); Anvari, Bahman [Department of Bioengineering, Rice University, Houston, TX 77251 (United States)


    Near-infrared wavelengths are absorbed less by epidermal melanin, and penetrate deeper into human skin dermis and blood than visible wavelengths. Therefore, laser irradiation using near-infrared wavelengths may improve the therapeutic outcome of cutaneous hyper-vascular malformations in moderately to heavily pigmented skin patients and those with large-sized blood vessels or blood vessels extending deeply into the skin. A mathematical model composed of a Monte Carlo algorithm to estimate the distribution of absorbed light, numerical solution of a bio-heat diffusion equation to calculate the transient temperature distribution, and a damage integral based on an empirical Arrhenius relationship to quantify the tissue damage was utilized to investigate the opto-thermal response of human skin to near-infrared and visible laser irradiations in conjunction with cryogen spray cooling. In addition, the thermal effects of a single continuous laser pulse and micropulse-composed laser pulse profiles were compared. Simulation results indicated that a 940 nm wavelength induces improved therapeutic outcome compared with a 585 and 595 nm wavelengths for the treatment of patients with large-sized blood vessels and moderately to heavily pigmented skin. On the other hand, a 585 nm wavelength shows the best efficacy in treating small-sized blood vessels, as characterized by the largest laser-induced blood vessel damage depth compared with 595 and 940 nm wavelengths. Dermal blood content has a considerable effect on the threshold incident dosage for epidermal damage, while the effect of blood vessel size is minimal. For the same macropulse duration and incident dosage, a micropulse-composed pulse profile results in higher peak temperature at the basal layer of skin epidermis than an ideal single continuous pulse profile.

  5. Experimental and theoretical investigations on the release and propagation of heavy gas; Experimentelle und theoretische Untersuchungen zur Schwergasfreisetzung und -ausbreitung

    Energy Technology Data Exchange (ETDEWEB)

    Rauchegger, Christian


    The hazardous potential of accidental heavy gas releases, especially those involving flammable and toxic gases, is widely known. In order to predict the area in which these gases are in hazardous concentrations, an estimation of the dispersion of these gases must be carried out. While the hazardous area for flammable heavy gases is determined by the lower explosion limit (ca. > 1 vol.%), the release of toxic heavy gases can result in a much larger hazardous area, as toxic gases, even in very low concentrations (ca. < 3000 ppm), have the potential to be highly damaging. The VDI guideline 3783, which is considered as state-of-the-art in Germany, can be used to estimate the dispersion of heavy gases. However, VDI 3783 gives no method for the prediction of the height and width of a heavy gas cloud, which are both required for quantitative risk analysis as well as for a possible coupling of a Lagrangian particle model with the VDI 3783 heavy gas dispersion model. Therefore, further calculation methods were used to describe these dimensions and were evaluated against, experimental studies of the length, width and height of the heavy and neutral gas field. The influence of the source height on the heavy gas dispersion was also investigated. It was found that elevating the source leads to a reduction of the length of the heavy gas area. Once the source reaches a critical height, a heavy gas area at ground level no longer exists. Therefore, for release heights above the critical height, heavy gas dispersion effects can be neglected and the calculation of the heavy gas area according to VDI 3783 part 2 is therefore no longer necessary. The release of heavy gases can occur from a process plant as well as from a standard gas bottle. For the release of heavy gases from standard gas bottles, a mathematical model has been developed to predict the time-dependent mass flow. This model takes into account the time-dependent temperature distribution of the bottle wall, and contains a

  6. Theoretical and experimental investigations of hot filter materials. Final report; Theoretische und experimentelle Untersuchungen zur Einsatzneignung von Heissgasfiltermaterialien. Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, B.; Angermann, J.


    Second generation fluidised bed combustors have higher gas turbine inlet temperatures and thus higher efficiencies. High-temperature filters are required for dust filtering of the hot flue gases and/or combustion gases. Several circuit and process variants are discussed on the basis of the first generation combined cycle process. Requirements on ceramic filters are listed, and experience with existing filter systems is presented. SiC-based filter materials are investigated with a view to their performance in hot gas filtering in pressurised fluidised bed systems. Three different SiC material types are analysed which differ in terms of their preparation conditions: Clay-bound SiC, liquid phase sintered SiC (LPS-SiC), and recrystallised SiC (RSiC). Both commercial materials and newly developed or advanced materials from the partnering Fraunhofer Institutes were used. The materials were found to undergo strong modifications subject to the type of material and the gas atmosphere. Liquid-phase sintered SiC generally had more pronounced effects than the other materials, owing to its smaller grain and pore size, which results in a much larger inner surface. (orig.) [German] Die Druckwirbelschichtfeuerung (DWSF) der so genannten 2. Generation zeichnet sich gegenueber herkoemmlichen DWSF-Konzepten durch hoehere Gasturbinen-Eintrittstemperaturen und dementsprechend hoehere Wirkungsgrade aus. Grundlegende Voraussetzung fuer die Realisierung des Prozesses ist jedoch die Verfuegbarkeit von Hochtemperaturfiltern fuer die Entstaubung der heissen Rauch- und/oder Brenngase. Ausgehend vom Druckwirbelschicht GuD-Prozess der 1. Generation werden verschiedene in der Literatur beschriebene Schaltungs- und Prozessvarianten vorgestellt und diskutiert. Die Anforderungen zum Einsatz keramischer Filterelemente fuer die Heissgasreinigung werden abgeleitet und Betriebserfahrungen mit bereits bestehenden Filteranlagen beschrieben. Das Ziel dieser Arbeit ist die Bewertung verschiedener Si

  7. Experimental and theoretical investigations of cadmium diffusion in vacancy-rich Cu(In, Ga)Se2 material (United States)

    Biderman, Norbert J.

    Copper indium gallium selenide (Cu(In,Ga)Se2 or CIGS) has become a significant topic of research and development for photovoltaic application. CIGS photovoltaic devices have demonstrated record conversion efficiencies however are still below the maximum solar conversion efficiency. Losses in performance have been attributed structural defects including vacancies, doping, grain boundaries, and compositional non-uniformity that are poorly understood and controlled. The cadmium sulfide (CdS) buffer layer plays a critical role in high-performance CIGS photovoltaic devices, serving as the n-type component of the p-n junction formed with the p-type CIGS absorber layer. Cadmium diffusion into the CIGS surface during CdS deposition creates a buried p-n homojunction in addition to the CIGS/CdS p-n heterojunction. CdS is believed to assist in reducing carrier recombination at the CIGS/CdS interface, an important attribute of high-efficiency solar cells. In the present work, cadmium diffusion mechanisms in CIGS are experimentally investigated via secondary ion mass spectroscopy (SIMS) and Auger electron spectroscopy (AES). Two cadmium diffusion profiles with distinct Arrhenius diffusion kinetics within a single depth profile of the CIGS thin film are observed with SIMS and AES: an intense first-stage diffusion profile directly below the CIGS/CdS interface and a long-range, second-stage diffusion profile that extends deep into the thin film. Cadmium grain boundary diffusion is also detected in fine-grain CIGS samples. These multiple diffusion processes are quantified in the present work, and the two-stage cadmium diffusion profiles suggest distinctive lattice diffusion mechanisms. Calculations and modeling of general impurity diffusion via interstitial sites in CIGS are also conducted via numerical including cadmium, iron, and zinc. In the numerical simulations, the standard diffusion-reaction kinetics theory is extended to vacancy-rich materials like CIGS that contain 1 at

  8. SU-E-T-748: Theoretical Investigation On Using High Energy Proton Beam for Total-Body-Irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, M; Zou, J; Chen, T; Yue, N [Robert Wood Johnson University Hospital, Rutgers University, New Brunswick, NJ (United States)


    Purpose: The broad-slow-rising entrance dose region proximal to the Bragg peak made by a mono-energetic proton beam could potentially be used for total body irradiation (TBI). Due to the quasi-uniform dose deposition, customized thickness compensation may not be required to deliver a uniform dose to patients with varied thickness. We investigated the possibility, efficacy, and hardware requirement to use such proton beam for TBI. Methods: A wedge shaped water phantom with thickness varying from 2 cm to 40 cm was designed to mimic a patient. Geant4 based Monte Carlo code was used to simulate broad mono-energetic proton beams with energy ranging from 250 MeV to 300 MeV radiating the phantom. A 6 MV photon with 1 cm water equivalent build-up used for conventional TBI was also calculated. A paired-opposing beam arrangement with no thickness compensation was used to generate TBI plans for all beam energies. Dose from all particles were scored on a grid size of 2 mm{sup 3}. Dose uniformity across the phantom was calculated to evaluate the plan. The field size limit and the dose uniformity of Mevion S250 proton system was examined by using radiochromic films placed at extended treatment distance with the open large applicator and 90° gantry angle. Results: To achieve a maximum ± 7.5% dose variation, the largest patient thickness variation allowed for 250 MeV, 275 MeV, and 300 MeV proton beams were 27.0 cm, 34.9 cm and 36.7 cm. The value for 6 MV photon beam was only 8.0 cm to achieve the same dose variation. With open gantry, Mevion S250 system allows 5 m source-to-surface distance producing an expected 70 cm{sup 2} field size. Conclusion: Energetic proton beam can potentially be used to deliver TBI. Treatment planning and delivery would be much simple since no thickness compensation is required to achieve a uniform dose distribution.

  9. Investigation of different extraction procedures for the determination of major and trace elements in coal by ICP-AES and ion chromatography

    Directory of Open Access Journals (Sweden)

    Tasić Aleksandra M.


    Full Text Available This paper presents the extraction of major and trace elements from a coal sample, in deionized water, by using three different extraction techniques. Rotary mixing and ultrasonic extraction were examined for different extraction times, while the microwave assisted extraction was performed at different temperatures. Metal concentrations (Na, K, Ca, Mg, Al, Fe, Mn, Be, Cd, Co, Cr, Hg, As, Ni, Se, Sb and Pb in a solution were determined by employing the inductively coupled plasma atomic emission spectrometry; whereas the results obtained for Na, K, Ca and Mg were compared employing ion chromatography. Comparing the rotary and ultrasonic-assisted extraction it is shown that the former is more efficient for the determination of Fe, Na and Pb, whereas the latter one has proven more efficient for the determination of Co and Cr ions. Microwave-assisted extraction has proven the most efficient method for any elements tested in coal. In addition, sequential extraction of elements was done using microwave digestion. The results of sequential extraction experiments indicated associations of investigated elements with a mineral phase and organic matrix. Sequential extraction provided information on possible leaching of As, Cd, Co, Cr, Ni, Pb, Fe and Mn in environmental conditions. [Projekat Ministarstva nauke Republike Srbije, br. 172030

  10. Investigation of interpolation techniques for the reconstruction of the first dimension of comprehensive two-dimensional liquid chromatography-diode array detector data. (United States)

    Allen, Robert C; Rutan, Sarah C


    Simulated and experimental data were used to measure the effectiveness of common interpolation techniques during chromatographic alignment of comprehensive two-dimensional liquid chromatography-diode array detector (LC×LC-DAD) data. Interpolation was used to generate a sufficient number of data points in the sampled first chromatographic dimension to allow for alignment of retention times from different injections. Five different interpolation methods, linear interpolation followed by cross correlation, piecewise cubic Hermite interpolating polynomial, cubic spline, Fourier zero-filling, and Gaussian fitting, were investigated. The fully aligned chromatograms, in both the first and second chromatographic dimensions, were analyzed by parallel factor analysis to determine the relative area for each peak in each injection. A calibration curve was generated for the simulated data set. The standard error of prediction and percent relative standard deviation were calculated for the simulated peak for each technique. The Gaussian fitting interpolation technique resulted in the lowest standard error of prediction and average relative standard deviation for the simulated data. However, upon applying the interpolation techniques to the experimental data, most of the interpolation methods were not found to produce statistically different relative peak areas from each other. While most of the techniques were not statistically different, the performance was improved relative to the PARAFAC results obtained when analyzing the unaligned data.

  11. The interplay of skeletal deformations and ultrafast excited-state intramolecular proton transfer: Experimental and theoretical investigation of 10-hydroxybenzo[h]quinoline

    Energy Technology Data Exchange (ETDEWEB)

    Schriever, Christian [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany)], E-mail:; Barbatti, Mario [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria)], E-mail:; Stock, Kai [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany); Aquino, Adelia J.A.; Tunega, Daniel [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria); Lochbrunner, Stefan [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany); Riedle, Eberhard [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany)], E-mail:; Vivie-Riedle, Regina de [Department Chemie - Ludwig-Maximilians-Universitaet (LMU), Butenandt-Strasse 11, 81377 Muenchen (Germany)], E-mail:; Lischka, Hans [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria)], E-mail:


    The excited-state intramolecular proton transfer in the aromatic polycycle 10-hydroxybenzo[h]quinoline is investigated by means of transient absorption experiments with 30 fs time resolution, classical dynamics and wavepacket dynamics. The experiments establish the ultrafast transfer after UV excitation and show signatures of coherent vibrational motion in the keto product. To elucidate details of the proton transfer mechanism, the classical dynamics is also performed for 2-(2'-hydroxyphenyl)benzothiazole and the results are compared. For both systems the proton transfer takes place on the ultrafast scale of 30-40 fs, with good agreement between the theoretical investigations and the measurements. The dynamics simulations show that for both molecules the proton is handed over by means of skeletal deformation of the molecule. Due to the more rigid structure of 10-hydroxybenzo[h]quinoline the hydrogen migration mode participates more actively than in 2-(2'-hydroxyphenyl)benzothiazole.

  12. Theoretical Investigation on Internal Leakage and Its Effect on the Efficiency of Fluid Switcher-Energy Recovery Device for Reverse Osmosis Desalting Plant

    Institute of Scientific and Technical Information of China (English)

    乞炳蔚; 王越; 王照成; 张燕平; 徐世昌; 王世昌


    This work is focused on the theoretical investigation of internal leakage of a newly developed pi-lot-scale fluid switcher-energy recovery device (FS-ERD) for reverse osmosis (RO) system. For the purpose of in-creasing FS-ERD efficiency and reducing the operating cost of RO, it is required to control the internal leakage in a low level. In this work, the internal leakage rates at different leakage gaps and retentate brine pressures are investi-gated by computational fluid dynamics (CFD) method and validating experiments. It is found that the internal leak-age has a linear relationship with the retentate brine pressure and a polynomial relationship with the scale of leakage gap. The results of the present work imply that low internal leakage and high retentate brine pressure bring benefits to achieve high FS-ERD efficiency.

  13. Unraveling the mystery of natural rubber biosythesis part I: investigation of the composition and growth of in vitro natural rubber using high resolution size exclusion chromatography (United States)

    Monitoring the growth of in vitro natural rubberwas accomplished by high resolution size exclusion chromatography, SEC.Washed rubber particles isolated from H. brasiliensis latex, containing the rubber transferase enzyme, were used to catalyze the polymerization of synthetic isopentenyl pyrophosphat...

  14. Theoretical Investigations Regarding Single Molecules

    DEFF Research Database (Denmark)

    Pedersen, Kim Georg Lind

    Neoclassical Valence Bond Theory, Quantum Transport, Quantum Interference, Kondo Effect, and Electron Pumping. Trap a single organic molecule between two electrodes and apply a bias voltage across this "molecular junction". When electrons pass through the molecule, the different electron paths can...

  15. Reactivity Differences between [alpha, beta]-Unsaturated Carbonyls and Hydrazones Investigated by Experimental and Theoretical Electron Density and Electron Localizability Analyses

    Energy Technology Data Exchange (ETDEWEB)

    Grabowsky, Simon; Weber, Manuela; Jayatilaka, Dylan; Chen, Yu-Sheng; Grabowski, Matthias T.; Brehme, Rainer; Hesse, Malte; Schirmeister, Tanja; Luger, Peter (UWA); (Wurzburg); (UC); (Berlin)


    It is still a challenge to predict a compound's reactivity from its ground-state electronic nature although Bader-type topological analyses of the electron density (ED) and electron localizability indicator (ELI) give detailed and useful information on electron concentration and electron-pair localization, respectively. Both ED and ELI can be obtained from theoretical calculations as well as high-resolution X-ray diffraction experiments. Besides ED and ELI descriptors, the delocalization index is used here; it is likewise derived from theoretical calculations as well as from experimental X-ray results, but in the latter case, demonstrated here for the first time. We investigate {alpha},{beta}-unsaturated carbonyl and hydrazone compounds because resonance exhibited by these compounds in the electronic ground-state determines their reactive behavior. The degree of resonance as well as the reactivity contrast are quantified with the electronic descriptors. Moreover, competitive mesomeric substituent effects are studied using the two biologically important compounds acrolein and acrylamide. The reactivity differences predicted from the analyses are in line with the known reactivity of these compounds in organic synthesis. Hence, the capability of the ED and ELI for rationalizing and predicting different and competing substituent effects with respect to reactivity is demonstrated.

  16. Green chromatography. (United States)

    Płotka, Justyna; Tobiszewski, Marek; Sulej, Anna Maria; Kupska, Magdalena; Górecki, Tadeusz; Namieśnik, Jacek


    Analysis of organic compounds in samples characterized by different composition of the matrix is very important in many areas. A vast majority of organic compound determinations are performed using gas or liquid chromatographic methods. It is thus very important that these methods have negligible environmental impact. Chromatographic techniques have the potential to be greener at all steps of the analysis, from sample collection and preparation to separation and final determination. The paper summarizes the approaches used to accomplish the goals of green chromatography. While complete elimination of sample preparation would be an ideal approach, it is not always practical. Solventless extraction techniques offer a very good alternative. Where solvents must be used, the focus should be on the minimization of their consumption. The approaches used to make chromatographic separations greener differ depending on the type of chromatography. In gas chromatography it is advisable to move away from using helium as the carrier gas because it is a non-renewable resource. GC separations using low thermal mass technology can be greener because of energy savings offered by this technology. In liquid chromatography the focus should be on the reduction of solvent consumption and replacement of toxic and environmentally hazardous solvents with more benign alternatives. Multidimensional separation techniques have the potential to make the analysis greener in both GC and LC. The environmental impact of the method is often determined by the location of the instrument with respect to the sample collection point.

  17. Ion Chromatography. (United States)

    Mulik, James D.; Sawicki, Eugene


    Accurate for the analysis of ions in solution, this form of analysis enables the analyst to directly assay many compounds that previously were difficult or impossible to analyze. The method is a combination of the methodologies of ion exchange, liquid chromatography, and conductimetric determination with eluant suppression. (Author/RE)

  18. Theoretical investigation of high velocity, temperature compensated Rayleigh waves along AlN/SiC substrates for high sensitivity mass sensors (United States)

    Caliendo, Cinzia


    The operation of electroacoustic devices based on surface acoustic waves (SAW) propagation along β-SiC/AlN and amorphous-SiC/AlN substrates is theoretically studied with respect to the AlN film thickness, the SAW propagation direction, temperature and electric boundary conditions. GHz-range, enhanced electroacoustic coupling coefficient, temperature compensated around 20 °C electroacoustic devices are the advantages of SiC/AlN composite structures. These structures are also suitable for the implementation of sensors with improved performances with respect to SAW devices based on bulk single crystal piezoelectric substrates. The structures feasibility was confirmed by structural investigation and quantitative analysis of sputtered amorphous-SiC and AlN films on Si substrates.

  19. Theoretical investigation of the electronic structure, optical, elastic and thermodynamics properties of a newly binary boron nitride (T-B3N3) (United States)

    Zhao, Shibo; Long, Jianping


    The ultrasoft pseudopotential planewave (UPPW) within density functional theory (DFT) has been used to investigate the electronic structure, optical, elastic and thermodynamics properties of newly binary boron nitride (T-B3N3). The calculated lattice parameters are in good agreement with previous theoretical results and deviated are less than 0.4%. The electronic structure showed that the T-B3N3 is metallic, and the optical spectra exhibit a noticeable anisotropy. The static dielectric constants, optical permittivity constants and the elastic properties are calculated. From our results, we observe that T-B3N3 is mechanically unstable and ductile. The entropy, enthalpy, free energy, heat capacity and Debye temperature of T-B3N3 was obtained. Up to now, there are no available experimental data about those properties. The results obtained in the present paper could provide important reference data for future studies.

  20. Theoretical investigation of InAs/GaSb type-II pin superlattice infrared detector in the mid wavelength infrared range (United States)

    Kaya, U.; Hostut, M.; Kilic, A.; Sakiroglu, S.; Sokmen, I.; Ergun, Y.; Aydinli, A.


    In this study, we present the theoretical investigation of type-II InAs/GaSb superlattice p-i-n detector. Kronig-Penney and envelope function approximation is used to calculate band gap energy and superlattice minibands. Variational method is also used to calculate exciton binding energies. Our results show that carriers overlap increases at GaSb/InAs interface on the higher energy side while it decreases at InAs/GaSb interface on the lower energy side with increasing reverse bias due to shifting the hole wavefunction toward to the GaSb/InAs interface decisively. Binding energies increase with increasing electric field due to overall overlap of electron and hole wave functions at the both interfaces in contrast with type I superlattices. This predicts that optical absorption is enhanced with increasing electric field.

  1. Influence of Nonpolar Substances on the Extraction Efficiency of Six Alkaloids in Zoagumhwan Investigated by Ultra Performance Liquid Chromatography and Photodiode Array Detection

    Directory of Open Access Journals (Sweden)

    Shijing Liu


    Full Text Available A reverse phase ultra performance liquid chromatography and photodiode array (UPLC-PDA detection method was established for the determination of six alkaloids in Zoagumhwan (ZGW, and further for investigating the influence of nonpolar substances on the extraction efficiency of these alkaloids. The method was based on a BEH C18 (50 mm × 2.1 mm, 1.7 μm column and mobile phase of aqueous phosphoric acid and acetonitrile including 0.05% buffer solution under gradient elution. ZGW samples of ZGW I, II, III and IV were obtained and prepared by pre-processing the crude materials of Coptidis rhizoma and Evodiae fructus using four technologies, namely direct water decoction, removal of nonpolar substances in Evodiae fructus by supercritical fluid extraction (SFE, removal of nonpolar substances in ZGW by SFE and removal of nonpolar substances in ZGW by steam distillation. The developed and validated UPLC-PDA method was precise, accurate and sensitive enough based on the facts that the six alkaloids showed good regression (r > 0.9998, the limit of detections and quantifications for six alkaloids were less than 28.8 and 94.5 ng/mL, respectively, and the recovery was in the range of 98.56%–103.24%. The sequence of the total contents of six alkaloids in these samples was ZGW II > ZGW IV > ZGW III > ZGW I. ZGW II, in which nonpolar substances, including essential oils, were firstly removed from Evodiae fructus by SFE, had the highest content of the total alkaloids, indicating that extraction efficiency of the total alkaloids could be remarkably increased after Evodiae fructus being extracted by SFE.

  2. Review: Applications of chromatography in forensic sciences

    Directory of Open Access Journals (Sweden)

    Manoj S. Charde


    Full Text Available This article reviews the use of different Chromatography techniques in the forensic science, Chromatographic technique is very sensitive and selective. Different types of chromatography techniques used were Liquid chromatography -mass spectrometry, Gas chromatography–mass spectrometry, Thin layer chromatography, HPTLC in investigating criminal cases of which chemical warfare’s, terrorist attacks, smugglers, drug abuse, alcoholics. This techniques are promising to detect even pictogram or very less, with selectivity and sensitivity.

  3. Theoretical and experimental investigations on the optimal match between compressor and cold finger of the Stirling-type pulse tube cryocooler (United States)

    Dang, Haizheng; Tan, Jun; Zhang, Lei


    The match between the pulse tube cold finger (PTCF) and the linear compressor of the Stirling-type pulse tube cryocooler plays a vital role in optimizing the compressor efficiency and in improving the PTCF cooling performance as well. In this paper, the interaction of them has been analyzed in a detailed way to reveal the match mechanism, and systematic investigations on the two-way matching have been conducted. The design method of the PTCF to achieve the optimal matching for the given compressor and the counterpart design method of the compressor to achieve the optimal matching for the given PTCF are put forward. Specific experiments are then carried out to verify the conducted theoretical analyses and modeling. For a given linear compressor, a new in-line PTCF which seeks to achieve the optimal match is simulated, designed and tested. And for a given coaxial PTCF, a new dual-opposed moving-coil linear compressor is also developed to match with it. The simulated and experimental results are compared, and fairly good agreements are found between them in both cases. The matched in-line cooler with the newly-designed PTCF has capacities of 4-11.84 W at 80 K with higher than 17% of Carnot efficiency and the mean motor efficiency of 81.5%, and the matched coaxial cooler with the new-designed compressor can provide 2-5.5 W at 60 K with higher than 9.6% of Carnot efficiency and the mean motor efficiency of 83%, which verify the validity of the theoretical investigations on the optimal match and the proposed design methods.

  4. Theoretical investigations on improving performance of cooling systems for fuel cell vehicles; Theoretische Untersuchungen zur Kuehlleistungssteigerung durch innovative Kuehlsysteme fuer Brennstoffzellen-Elektrofahrzeuge

    Energy Technology Data Exchange (ETDEWEB)

    Reichler, Mark


    In this work theoretical investigations are carried out for cooling systems, which are used in fuel cell vehicles. This work focuses mainly on the capability of increasing the heat rejection rate by using new alternative cooling systems and by improving the conventional cooling system. Fuel cell vehicles have a higher demand of heat rejection to the ambient than comparable vehicles with combustion engine. The performance of conventional liquid cooling systems, especially at high loads and high ambient temperatures, is often not sufficient anymore. Hence, cooling systems with improved performance are necessary for fuel cell vehicles. The investigations in this work are based on DaimlerChrysler's ''A-Class'' having a PEM-Fuel Cell system integrated. Specific computational models are developed for radiators and condensers to evaluate the performance of different cooling concepts. The models are validated with experimental data. Based on an intensive investigation in the open literature the state of the art of cooling systems for fuel cell vehicles is depicted. Furthermore new cooling concepts as an alternative to the liquid cooling system are presented. The method of cooling the fuel cell by using two-phase transition shows the greatest capability to increase the cooling performance. Hence, this concept is investigated in detail. Two different concepts with three different refrigerants (R113, R245fa und R236fa) are analyzed. Cooling performance of this concept shows improvement of 18.2 up to 32.6 % compared to the conventional liquid cooling system. Thus, a two phase cooling system represents an alternative cooling system for fuel cell vehicles, which should be closer investigated by experiments. (orig.)

  5. 3-methylcyclohexanone thiosemicarbazone: determination of E/Z isomerization barrier by dynamic high-performance liquid chromatography, configuration assignment and theoretical study of the mechanisms involved by the spontaneous, acid and base catalyzed processes. (United States)

    Carradori, Simone; Cirilli, Roberto; Dei Cicchi, Simona; Ferretti, Rosella; Menta, Sergio; Pierini, Marco; Secci, Daniela


    Here, we report on the simultaneous direct HPLC diastereo- and enantioseparation of 3-methylcyclohexanone thiosemicarbazone (3-MCET) on a polysaccharide-based chiral stationary phase under normal-phase conditions. The optimized chromatographic system was employed in dynamic HPLC experiments (DHPLC), as well as detection technique in a batch wise approach to determine the rate constants and the corresponding free energy activation barriers of the spontaneous, base- and acid-promoted E/Z diastereomerization of 3-MCET. The stereochemical characterization of four stereoisomers of 3-MCET was fully accomplished by integrating the results obtained by chemical correlation method with those derived by theoretical calculations and experimental investigations of circular dichroism (CD). As a final goal, a deepened analysis of the perturbing effect exercised by the stationary phase on rate constant values measured through DHPLC determinations as a function of the chromatographic separation factor α of the interconverting species was successfully accomplished. This revealed quite small deviations from the equivalent kinetic values obtained by off-column batch wise procedure, and suggested a possible effective correction of rate constants measured by DHPLC approach.

  6. Removal of halogenated emerging contaminants from water by nitrogen-doped graphene decorated with palladium nanoparticles: Experimental investigation and theoretical analysis. (United States)

    Li, Lei; Gong, Li; Wang, Yi-Xuan; Liu, Qi; Zhang, Jie; Mu, Yang; Yu, Han-Qing


    The removal performance and mechanisms of halogenated emerging contaminants from water by palladium decorated nitrogen-doped graphene (Pd/NG) were investigated in this study. For comparison, three catalysts of Pd/NG, palladium decorated graphene (Pd/G) and commercial Pd/C were initially explored to degrade tetrabromobisphenol A (TBBPA). After that, the influence of various environmental parameters on TBBPA removal by the Pd/NG catalyst was evaluated. Moreover, both Langmuir-Hinshelwood model and density functional theory (DFT) were adopted to theoretically elucidate the adsorption and the activation of TBBPA on the catalyst. The results show that the apparent rate constant of TBBPA dehalogenation was increased by 26.7% and 39.0% in the presence of the Pd/NG catalyst compared to the Pd/G and Pd/C ones. Higher temperature, catalyst dosage and alkaline conditions resulted in the enhancement of TBBPA dehalogenation by the Pd/NG catalyst, while humic acid in the solution had a negatively effect on the transformation of TBBPA. The corresponding rate constant value exhibited a 2.1- and 1.8-fold increase with the rise of temperature from 298 to 328 K and initial pH from 6.5 to 9.0, respectively. On the contrary, the rate constant was decreased by 78.9% in the presence of 15 mg L(-1) humic acid. Theoretical analysis revealed that both adsorption and activation processes of TBBPA on the Pd/NG catalyst were enhanced through the N doping into graphene framework.

  7. Theoretical and experimental investigations of optical, structural and electronic properties of the lower-dimensional hybrid [NH3-(CH2)10-NH3]ZnCl4 (United States)

    El Mrabet, R.; Kassou, S.; Tahiri, O.; Belaaraj, A.; Guionneau, P.


    In the current study, a combination between theoretical and experimental studies has been made for the hybrid perovskite [NH3-(CH2)10-NH3]ZnCl4. The density functional theory (DFT) was performed to investigate structural and electronic properties of the tilted compound. A local approximation (LDA) and semi-local approach (GGA) were employed. The results are obtained using, respectively, the local exchange correlation functional of Perdew-Wang 92 (PW92) and semi local functional of Perdew-Burke-Ernzerhof (PBE). The optimized cell parameters are in good agreement with the experimental results. Electronic properties have been studied through the calculation of band structures and density of state (DOS), while structural properties are investigated by geometry optimization of the cell. Fritz-Haber-Institute (FHI) pseudopotentials were employed to perform all calculations. The optical diffuse reflectance spectra was mesured and applied to deduce the refractive index ( n), the extinction coefficient ( k), the absorption coefficient (α), the real and imaginary dielectric permittivity parts (ɛr,ɛi)) and the optical band gap energy Eg. The optical band gap energy value shows good consistent with that obtained from DFT calculations and reveals the insulating behavior of the material.

  8. Investigation of amino acid δ 13C signatures in bone collagen to reconstruct human palaeodiets using liquid chromatography-isotope ratio mass spectrometry (United States)

    Choy, Kyungcheol; Smith, Colin I.; Fuller, Benjamin T.; Richards, Michael P.


    This research presents the individual amino acid δ 13C values in bone collagen of humans ( n = 9) and animals ( n = 27) from two prehistoric shell midden sites in Korea. We obtained complete baseline separation of 16 of the 18 amino acids found in bone collagen by using liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). The isotopic results reveal that the humans and animals in the two sites had similar patterns in essential amino acids (EAAs) and non-essential amino acids (NEAAs). The EAA and NEAA δ 13C values in humans are intermediate between those in marine and terrestrial animals. However, the threonine δ 13C values in humans and animals measured in this study are more highly enriched than those of other amino acids. At both sites, all amino acids in marine animals are 13C-enriched relative to those of the terrestrial animals. The isotopic evidence suggests that the Tongsamdong human had EAAs and NEAAs from marine food resources, while the Nukdo humans mainly had EAAs from terrestrial food resources but obtained NEAAs from both terrestrial and marine resources. The δ 13C isotopic differences in amino acids between marine and terrestrial animals were the largest for glycine (NEAA) and histidine (EAA) and the smallest for tyrosine (NEAA) and phenylalanine (EAA). In addition, threonine among the EAAs also had a large difference (˜8‰) in δ 13C values between marine and terrestrial animals, and has the potential to be used as an isotopic marker in palaeodietary studies. Threonine δ 13C values were used in conjunction with the established Δ 13C Glycine-phenylalanine values and produced three distinct dietary groups (terrestrial, omnivorous, and marine). In addition, threonine δ 13C values and Δ 13C Serine-phenylalanine values were discovered to separate between two dietary groups (terrestrial vs. marine), and these δ 13C values may provide a potential new indicator for investigating the distinction between marine and terrestrial protein

  9. Theoretical investigations of the spin-Hamiltonian parameters and local structural distortion of Fe(3+): ZnAl2O4 crystals. (United States)

    Yang, Zi-Yuan


    The relations between the spin-Hamiltonian (SH) parameters and the structural parameters of the Fe(3+) ions in Fe(3+): ZnAl2O4 crystals have been established by means of the microscopic spin Hamiltonian theory and the superposition model (SPM). On the basis of this, the local structure distortion, the second-order zero-field splitting (ZFS) parameter D, the fourth-order ZFS parameter (a-F), and the Zeeman g-factors g factors: g//, g⊥, and Δg(=g//-g⊥) for Fe(3+) ions in Fe(3+): ZnAl2O4 crystals, for the first time taking into account the electronic magnetic interactions, i.e. the spin-spin (SS), the spin-other-orbit (SOO), and the orbit-orbit (OO) interactions, besides the well-known spin-orbit (SO) interaction, are theoretically investigated using complete diagonalization method (CDM). This investigation reveals that the local structure distortion effect plays an important role in explaining the spectroscopic properties of Fe(3+) ions in Fe(3+): ZnAl2O4 crystals. The theoretical second-order ZFS parameter D, the fourth-order ZFS parameter (a-F), and the Zeeman g-factors: g//, g⊥, and Δg of the ground state for Fe(3+) ion in Fe(3+): ZnAl2O4 crystals yield a good agreement with experiment findings by taking into account the lattice distortions: ΔR=0.0191nm and Δθ=0.076°. In conclusion, our research shows that there is a slight local structure distortion for Fe(3+) ions in Fe(3+): ZnAl2O4 crystals, but the site of Fe(3+) still retains D3d symmetry. On the other hand, it is found for Fe(3+) ions in Fe(3+): ZnAl2O4 crystals that the SO mechanism is the most important one, whereas the contributions to the SH parameters from other four mechanisms, including the SS, SOO, OO, and SO∼SS∼SOO∼OO mechanisms are not appreciable, especially for the ZFS parameter D.

  10. Theoretical investigation of water oxidation processes on small Mn(x)Ti(2-x)O4 (x = 0-2) complexes. (United States)

    Lee, Choongkeun; Aikens, Christine M


    Understanding the water oxidation process on small metal oxide complexes is fundamental for developing photocatalysts for solar fuel production. Titanium oxide and manganese oxide complexes have high potential as components of a cheap, nontoxic, and stable photocatalyst. In this theoretical work, the water oxidation process on Mn(x)Ti(2-x)O4 (x = 0-2) clusters is investigated at the BP86 level of theory using two water molecules and fully saturated systems. In the oxidation cycle using two water molecules, Mn reduces the reaction energy; however, Mn does not reduce the reaction energy on the fully saturated system. When two water molecules are used, the highest reaction energy in the water oxidation cycle is lower than 3 eV, but the highest reaction energy is higher than 3 eV on fully saturated systems except for the pure titanium oxide complex which has a highest reaction energy of 2.56 eV. Dehydrogenation processes in the water oxidation cycle require higher energy than the O-O formation or water adsorption processes. The overall dehydrogenation energy is usually smaller on complexes including at least one Mn atom and it is smallest on the Mn2O4 complex that has two water molecules. Considering the highest reaction energy in the overall water oxidation cycle, water oxidation at the manganese atom of MnTiO4 hydrated with two water molecules is the most favorable in energy.

  11. Tetrathiafulvalene-1,3,5-triazines as (multi)donor-acceptor systems with tunable charge transfer: structural, photophysical, and theoretical investigations. (United States)

    Pop, Flavia; Riobé, François; Seifert, Sabine; Cauchy, Thomas; Ding, Jie; Dupont, Nathalie; Hauser, Andreas; Koch, Marius; Avarvari, Narcis


    Palladium-catalyzed cross-coupling reactions between chlorinated 1,3,5-triazines (TZ) and tetrathiafulvalene (TTF) trimethyltin derivatives afford mono- and C3 symmetric tris(TTF)-triazines as donor-acceptor compounds in which the intramolecular charge transfer (ICT) is modulated by the substitution scheme on TTF and TZ and by chemical or electrochemical oxidation. The TTF-TZ-Cl2 and (SMe)2TTF-TZ-Cl2 derivatives show fully planar structures in the solid state as a consequence of the conjugation between the two units. Electrochemical and photophysical investigations, supported by theoretical calculations, clearly demonstrate that the lowest excited state can be ascribed to the intramolecular charge transfer (ICT) π(TTF)→π*(TZ) transition. The tris(TTF) compound [(SMe)2TTF]3-TZ shows fluorescence when excited in the ICT band, and the emission is quenched upon oxidation. The radical cations TTF(+•) are easily observed in all of the cases through chemical and electrochemical oxidation by steady-state absorption experiments. In the case of [(SMe)2TTF]3-TZ, a low energy band at 5000 cm(-1), corresponding to a coupling between TTF(+•) and TTF units, is observed. A crystalline radical cation salt with the TTF-TZ-Cl2 donor and PF6(-) anion, prepared by electrocrystallization, is described.

  12. Toward the microscopic identification of anions and cations at the ionic liquid|Ag(111) interface: a combined experimental and theoretical investigation. (United States)

    Buchner, Florian; Forster-Tonigold, Katrin; Uhl, Benedikt; Alwast, Dorothea; Wagner, Nadja; Farkhondeh, Hanieh; Gross, Axel; Behm, R Jürgen


    The interaction between an adsorbed 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMP][TFSA], ionic liquid (IL) layer and a Ag(111) substrate, under ultrahigh-vacuum conditions, was investigated in a combined experimental and theoretical approach, by high-resolution scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and dispersion-corrected density functional theory calculations (DFT-D). Most importantly, we succeeded in unambiguously identifying cations and anions in the adlayer by comparing experimental images with submolecular resolution and simulated STM images based on DFT calculations, and these findings are in perfect agreement with the 1:1 ratio of anions and cations adsorbed on the metal derived from XPS measurements. Different adlayer phases include a mobile 2D liquid phase at room temperature and two 2D solid phases at around 100 K, i.e., a 2D glass phase with short-range order and some residual, but very limited mobility and a long-range ordered 2D crystalline phase. The mobility in the different adlayer phases, including melting of the 2D crystalline phase, was evaluated by dynamic STM imaging. The DFT-D calculations show that the interaction with the substrate is composed of mainly van der Waals and weak electrostatic (dipole-induced dipole) interactions and that upon adsorption most of the charge remains at the IL, leading to attractive electrostatic interactions between the adsorbed species.

  13. Theoretical investigations on the defect structures and spin Hamiltonian parameters for various orthorhombic Rh2+ centres in KTiOPO4 and KTiOAsO4 (United States)

    Ding, Chang-Chun; Wu, Shao-Yi; Zhang, Li-Juan; Li, Guo-Liang; Zhang, Zhi-Hong


    The defect structures and spin Hamiltonian parameters (SHPs) for three Rh2+ centres (denoted C1 in KTiOAsO4 and C2 and C3 in KTiOPO4) are theoretically investigated by utilising the perturbation formulae for a 4d7 ion under orthorhombically (D2h) elongated octahedra. The defect structures are characterized by the axial elongation ratios of 4.91%, 4.93% and 4.90% along the Z axis and the planar bond length variation ratios of 0.05%, 0.01% and 0.04% for centres C1, C2 and C3, respectively, owing to the Jahn-Teller effect. The nearly identical moderate axial elongation ratios and the slightly different tiny planar bond length variation ratios may suitably account for the comparable moderate axial g anisotropies ∆g (≈0.6087, 0.6124 and 0.6067) and the slightly dissimilar tiny perpendicular g anisotropies δg (≈0.0649, 0.0097 and 0.0509) of the three centres, respectively. All centres demonstrate similar strong crystal-field interactions and moderate covalence arising from the comparable short impurity-ligand distances.

  14. Theoretical investigation of tensile strained GeSn waveguide with Si₃N₄ liner stressor for mid-infrared detector and modulator applications. (United States)

    Zhang, Qingfang; Liu, Yan; Yan, Jing; Zhang, Chunfu; Hao, Yue; Han, Genquan


    We theoretically investigate a tensile strained GeSn waveguide integrated with Si₃N₄ liner stressor for the applications in mid-infrared (MIR) detector and modulator. A substantial tensile strain is induced in a 1 × 1 μm² GeSn waveguide by the expansion of 500 nm Si₃N₄ liner stressor and the contour plots of strain are simulated by the finite element simulation. Under the tensile strain, the direct bandgap E(G,Γ) of GeSn is significantly reduced by lowering the Γ conduction valley in energy and lifting of degeneracy of valence bands. Absorption coefficients of tensile strained GeSn waveguides with different Sn compositions are calculated. As the Si₃N₄ liner stressor expands by 1%, the cut-off wavelengths of tensile strained Ge(0.97)Sn(0.03), Ge(0.95)Sn(0.05), and Ge(0.90)Sn(0.10) waveguide photodetectors are extended to 2.32, 2.69, and 4.06 μm, respectively. Tensile strained Ge(0.90)Sn(0.10) waveguide electro-absorption modulator based on Franz-Keldysh (FK) effect is demonstrated in theory. External electric field dependence of cut-off wavelength and propagation loss of tensile strained Ge(0.90)Sn(0.10) waveguide is observed, due to the FK effect.

  15. Systematic optimisation and evaluation of on-line, off-line and stop-flow comprehensive hydrophilic interaction chromatography×reversed phase liquid chromatographic analysis of procyanidins, part I: theoretical considerations. (United States)

    Kalili, Kathithileni M; de Villiers, André


    Comprehensive two-dimensional liquid chromatography (LC×LC) provides significantly improved separation for complex real-life samples. LC×LC can be performed in one of three different ways, using on-line, off-line, or stop-flow configurations. We have previously shown how off-line comprehensive hydrophilic interaction chromatography (HILIC)×reversed-phase liquid chromatography (RP-LC) provides a powerful separation system for procyanidins (PCs), one of the most complex fractions of natural phenolics. In the current contribution, a systematic approach for the optimisation and evaluation of each of the LC×LC methodologies is presented using HILIC×RP-LC analysis of PCs as application. Optimisation was performed using the peak capacities of individual one-dimensional separations measured for different gradient times and flow rates and their combination in each of the three LC×LC modes by taking into account the effects of first dimension under-sampling, the degree of orthogonality between the two dimensions and additional band broadening associated with stop-flow analysis. The performance of all three methods is compared in terms of practical peak capacities, analysis times and peak production rates. One-dimensional LC provided the best performance for separations requiring relatively low peak capacities, whereas the on-line LC×LC system was advantageous for required practical peak capacities up to ~600. For higher resolution, the off-line or stop-flow systems should be used. Especially noteworthy is the fact that, due to slow diffusion of PCs, the contribution of stop-flow to first dimension band broadening was negligible for stop-flow times of up to 15min. In a separate contribution, the experimental verification of the findings of this study will be reported.

  16. Gas Chromatography (United States)

    Qian, Michael C.

    Gas chromatography (GC) has many applications in the analysis of food products. GC has been used for the determination of fatty acids, triglycerides, cholesterol, gases, water, alcohols, pesticides, flavor compounds, and many more. While GC has been used for other food components such as sugars, oligosaccharides, amino acids, peptides, and vitamins, these substances are more suited to analysis by high performance liquid chromatography. GC is ideally suited to the analysis of volatile substances that are thermally stable. Substances such as pesticides and flavor compounds that meet these criteria can be isolated from a food and directly injected into the GC. For compounds that are thermally unstable, too low in volatility, or yield poor chromatographic separation due to polarity, a derivatization step must be done before GC analysis. The two parts of the experiment described here include the analysis of alcohols that requires no derivatization step, and the analysis of fatty acids which requires derivatization. The experiments specify the use of capillary columns, but the first experiment includes conditions for a packed column.

  17. A theoretical investigation of the influence of gold nanosphere size on the decay and energy transfer rates and efficiencies of quantum emitters

    Energy Technology Data Exchange (ETDEWEB)

    Marocico, Cristian A.; Zhang, Xia; Bradley, A. Louise, E-mail: [Semiconductor Photonics Group, School of Physics and CRANN, Trinity College Dublin, College Green, Dublin 2 (Ireland)


    We present in this contribution a comprehensive investigation of the effect of the size of gold nanospheres on the decay and energy transfer rates of quantum systems placed close to these nanospheres. These phenomena have been investigated before, theoretically and experimentally, but no comprehensive study of the influence of the nanoparticle size on important dependences of the decay and energy transfer rates, such as the dependence on the donor-acceptor spectral overlap and the relative positions of the donor, acceptor, and nanoparticle, exists. As such, different accounts of the energy transfer mechanism have been presented in the literature. We perform an investigation of the energy transfer mechanisms between emitters and gold nanospheres and between donor-acceptor pairs in the presence of the gold nanospheres using a Green’s tensor formalism, experimentally verified in our lab. We find that the energy transfer rate to small nanospheres is greatly enhanced, leading to a strong quenching of the emission of the emitter. When the nanosphere size is increased, it acts as an antenna, increasing the emission of the emitter. We also investigate the emission wavelength and intrinsic quantum yield dependence of the energy transfer to the nanosphere. As evidenced from the literature, the energy transfer process between the quantum system and the nanosphere can have a complicated distance dependence, with a r{sup −6} regime, characteristic of the Förster energy transfer mechanism, but also exhibiting other distance dependences. In the case of a donor-acceptor pair of quantum systems in the presence of a gold nanosphere, when the donor couples strongly to the nanosphere, acting as an enhanced dipole; the donor-acceptor energy transfer rate then follows a Förster trend, with an increased Förster radius. The coupling of the acceptor to the nanosphere has a different distance dependence. The angular dependence of the energy transfer efficiency between donor and

  18. A theoretical investigation of the influence of gold nanosphere size on the decay and energy transfer rates and efficiencies of quantum emitters. (United States)

    Marocico, Cristian A; Zhang, Xia; Bradley, A Louise


    We present in this contribution a comprehensive investigation of the effect of the size of gold nanospheres on the decay and energy transfer rates of quantum systems placed close to these nanospheres. These phenomena have been investigated before, theoretically and experimentally, but no comprehensive study of the influence of the nanoparticle size on important dependences of the decay and energy transfer rates, such as the dependence on the donor-acceptor spectral overlap and the relative positions of the donor, acceptor, and nanoparticle, exists. As such, different accounts of the energy transfer mechanism have been presented in the literature. We perform an investigation of the energy transfer mechanisms between emitters and gold nanospheres and between donor-acceptor pairs in the presence of the gold nanospheres using a Green's tensor formalism, experimentally verified in our lab. We find that the energy transfer rate to small nanospheres is greatly enhanced, leading to a strong quenching of the emission of the emitter. When the nanosphere size is increased, it acts as an antenna, increasing the emission of the emitter. We also investigate the emission wavelength and intrinsic quantum yield dependence of the energy transfer to the nanosphere. As evidenced from the literature, the energy transfer process between the quantum system and the nanosphere can have a complicated distance dependence, with a r(-6) regime, characteristic of the Förster energy transfer mechanism, but also exhibiting other distance dependences. In the case of a donor-acceptor pair of quantum systems in the presence of a gold nanosphere, when the donor couples strongly to the nanosphere, acting as an enhanced dipole; the donor-acceptor energy transfer rate then follows a Förster trend, with an increased Förster radius. The coupling of the acceptor to the nanosphere has a different distance dependence. The angular dependence of the energy transfer efficiency between donor and acceptor

  19. Mass transfer mechanism in chiral reversed phase liquid chromatography. (United States)

    Gritti, Fabrice; Guiochon, Georges


    The mechanism of mass transfer in chiral chromatography was investigated using an experimental protocol already applied in RPLC and HILIC chromatography. The different contributions to the reduced height equivalent to a theoretical plate (HETP) include the longitudinal diffusion HETP term, the solid-liquid mass transfer resistance HETP term, the short-range eddy dispersion HETP term, and the long-range eddy dispersion HETP term. Their accurate measurement permits the determination of the adsorption rate constant kads of trans-stilbene enantiomers on a column packed with Lux 5 μm Cellulose-1 particles. The experimental results demonstrate that the number of adsorption-desorption steps per unit time of chiral compounds on polysaccharide-based chiral stationary phases is four orders of magnitude smaller than that of achiral compounds.

  20. On the Experimental and Theoretical Investigations of Lean Partially Premixed Combustion, Burning Speed, Flame Instability and Plasma Formation of Alternative Fuels at High Temperatures and Pressures (United States)

    Askari, Omid

    This dissertation investigates the combustion and injection fundamental characteristics of different alternative fuels both experimentally and theoretically. The subjects such as lean partially premixed combustion of methane/hydrogen/air/diluent, methane high pressure direct-injection, thermal plasma formation, thermodynamic properties of hydrocarbon/air mixtures at high temperatures, laminar flames and flame morphology of synthetic gas (syngas) and Gas-to-Liquid (GTL) fuels were extensively studied in this work. These subjects will be summarized in three following paragraphs. The fundamentals of spray and partially premixed combustion characteristics of directly injected methane in a constant volume combustion chamber have been experimentally studied. The injected fuel jet generates turbulence in the vessel and forms a turbulent heterogeneous fuel-air mixture in the vessel, similar to that in a Compressed Natural Gas (CNG) Direct-Injection (DI) engines. The effect of different characteristics parameters such as spark delay time, stratification ratio, turbulence intensity, fuel injection pressure, chamber pressure, chamber temperature, Exhaust Gas recirculation (EGR) addition, hydrogen addition and equivalence ratio on flame propagation and emission concentrations were analyzed. As a part of this work and for the purpose of control and calibration of high pressure injector, spray development and characteristics including spray tip penetration, spray cone angle and overall equivalence ratio were evaluated under a wide range of fuel injection pressures of 30 to 90 atm and different chamber pressures of 1 to 5 atm. Thermodynamic properties of hydrocarbon/air plasma mixtures at ultra-high temperatures must be precisely calculated due to important influence on the flame kernel formation and propagation in combusting flows and spark discharge applications. A new algorithm based on the statistical thermodynamics was developed to calculate the ultra-high temperature plasma

  1. A theoretical and empirical investigation into the willingness-to-pay function for new innovative drugs by Germany's health technology assessment agency (IQWiG). (United States)

    Gandjour, Afschin


    Under the recently enacted pharmaceutical price and reimbursement regulation in Germany, new drugs are subject to a rapid assessment to determine whether there is sufficient evidence of added clinical benefits compared with the existing standard of treatment. If such added benefits are confirmed, manufacturers and representatives of the Statutory Health Insurance (SHI) are expected to negotiate an appropriate reimbursement price. If parties fail to reach an agreement, a final decision on the reimbursement price will be made by an arbitration body. If one of the parties involved wishes so, then the Institute for Quality and Efficiency in Health Care (Institut für Qualität und Wirtschaftlichkeit im Gesundheitswesen, IQWiG) will be commissioned with a formal evaluation of costs and benefits of the product in question. IQWiG will make a recommendation for a reimbursement price based on the 'efficiency frontier' in a therapeutic area. The purpose of the assessments is to provide support for decision-making bodies that act on behalf of the SHI insurants. To determine the willingness to pay for new drugs, IQWiG uses the following decision rule: the incremental cost-effectiveness ratio of a new drug compared with the next effective intervention should not be higher than that of the next effective intervention compared with its comparator. The purpose of this paper was to investigate the theoretical and empirical relationship between the willingness to pay for drugs and their health benefits. The analysis shows that across disease areas IQWiG has a curvilinear relationship between willingness to pay and health benefits. Future research may address the validity of the willingness-to-pay function from the viewpoint of the individual SHI insurants.

  2. A theoretical and experimental investigation of the spectroscopic properties of a DNA-intercalator salphen-type Zn(II) complex. (United States)

    Biancardi, Alessandro; Burgalassi, Azzurra; Terenzi, Alessio; Spinello, Angelo; Barone, Giampaolo; Biver, Tarita; Mennucci, Benedetta


    The photophysical and DNA-binding properties of the cationic zinc(II) complex of 5-triethylammonium methyl salicylidene ortho-phenylenediiminato (ZnL(2+)) were investigated by a combination of experimental and theoretical methods. DFT calculations were performed on both the ground and the first excited states of ZnL(2+) and on its possible mono- and dioxidation products, both in vacuo and in selected solvents mimicked by the polarizable continuum model. Comparison of the calculated absorption and fluorescence transitions with the corresponding experimental data led to the conclusion that visible light induces a two-electron photooxidation process located on the phenylenediiminato ligand. Kinetic measurements, performed by monitoring absorbance changes over time in several solvents, are in agreement with a slow unimolecular photooxidation process, which is faster in water and slower in less polar solvents. Moreover, structural details of ZnL-DNA binding were obtained by DFT calculations on the intercalation complexes between ZnL and the d(ApT)2 and d(GpC)2 dinucleoside monophosphate duplexes. Two main complementary binding interactions are proposed: 1) intercalation of the central phenyl ring of the ligand between the stacked DNA base pairs; 2) external electrostatic attraction between the negatively charged phosphate groups and the two cationic triethylammonium groups of the Schiff-base ligand. Such suggestions are supported by fluorescence titrations performed on the ZnL/DNA system at different ionic strengths and temperatures. In particular, the values of the DNA-binding constants obtained at different temperatures provided the enthalpic and entropic contributions to the binding and confirmed that two competitive mechanisms, namely, intercalation and external interaction, are involved. The two mechanisms are coexistent at room temperature under physiological conditions.

  3. MR guided thermal therapy of pancreatic tumors with endoluminal, intraluminal and interstitial catheter-based ultrasound devices: preliminary theoretical and experimental investigations (United States)

    Prakash, Punit; Salgaonkar, Vasant A.; Scott, Serena J.; Jones, Peter; Hensley, Daniel; Holbrook, Andrew; Plata, Juan; Sommer, Graham; Diederich, Chris J.


    Image-guided thermal interventions have been proposed for potential palliative and curative treatments of pancreatic tumors. Catheter-based ultrasound devices offer the potential for temporal and 3D spatial control of the energy deposition profile. The objective of this study was to apply theoretical and experimental techniques to investigate the feasibility of endogastric, intraluminal and transgastric catheter-based ultrasound for MR guided thermal therapy of pancreatic tumors. The transgastric approach involves insertion of a catheter-based ultrasound applicator (array of 1.5 mm OD x 10 mm transducers, 360° or sectored 180°, ~7 MHz frequency, 13-14G cooling catheter) directly into the pancreas, either endoscopically or via image-guided percutaneous placement. An intraluminal applicator, of a more flexible but similar construct, was considered for endoscopic insertion directly into the pancreatic or biliary duct. An endoluminal approach was devised based on an ultrasound transducer assembly (tubular, planar, curvilinear) enclosed in a cooling balloon which is endoscopically positioned within the stomach or duodenum, adjacent to pancreatic targets from within the GI tract. A 3D acoustic bio-thermal model was implemented to calculate acoustic energy distributions and used a FEM solver to determine the transient temperature and thermal dose profiles in tissue during heating. These models were used to determine transducer parameters and delivery strategies and to study the feasibility of ablating 1-3 cm diameter tumors located 2-10 mm deep in the pancreas, while thermally sparing the stomach wall. Heterogeneous acoustic and thermal properties were incorporated, including approximations for tumor desmoplasia and dynamic changes during heating. A series of anatomic models based on imaging scans of representative patients were used to investigate the three approaches. Proof of concept (POC) endogastric and transgastric applicators were fabricated and experimentally

  4. Comprehensive analysis of a multidimensional liquid chromatography mass spectrometry dataset acquired on a quadrupole selecting, quadrupole collision cell, time-of-flight mass spectrometer: I. How much of the data is theoretically interpretable by search engines? (United States)

    Chalkley, Robert J; Baker, Peter R; Hansen, Kirk C; Medzihradszky, Katalin F; Allen, Nadia P; Rexach, Michael; Burlingame, Alma L


    An in-depth analysis of a multidimensional chromatography-mass spectrometry dataset acquired on a quadrupole selecting, quadrupole collision cell, time-of-flight (QqTOF) geometry instrument was carried out. A total of 3269 CID spectra were acquired. Through manual verification of database search results and de novo interpretation of spectra 2368 spectra could be confidently determined as predicted tryptic peptides. A detailed analysis of the non-matching spectra was also carried out, highlighting what the non-matching spectra in a database search typically are composed of. The results of this comprehensive dataset study demonstrate that QqTOF instruments produce information-rich data of which a high percentage of the data is readily interpretable.

  5. Theoretical nuclear physics

    CERN Document Server

    Blatt, John M


    A classic work by two leading physicists and scientific educators endures as an uncommonly clear and cogent investigation and correlation of key aspects of theoretical nuclear physics. It is probably the most widely adopted book on the subject. The authors approach the subject as ""the theoretical concepts, methods, and considerations which have been devised in order to interpret the experimental material and to advance our ability to predict and control nuclear phenomena.""The present volume does not pretend to cover all aspects of theoretical nuclear physics. Its coverage is restricted to

  6. Theoretical and computational chemistry. (United States)

    Meuwly, Markus


    Computer-based and theoretical approaches to chemical problems can provide atomistic understanding of complex processes at the molecular level. Examples ranging from rates of ligand-binding reactions in proteins to structural and energetic investigations of diastereomers relevant to organo-catalysis are discussed in the following. They highlight the range of application of theoretical and computational methods to current questions in chemical research.

  7. A theoretical investigation of the structural and electronic properties of 55-atom nanoclusters: The examples of Y–Tc and Pt

    Energy Technology Data Exchange (ETDEWEB)

    Batista, Krys E. A.; Piotrowski, Maurício J., E-mail: [Department of Physics, Federal University of Pelotas, P.O. Box 354, 96010 − 900, Pelotas, RS (Brazil); Chaves, Anderson S.; Da Silva, Juarez L. F., E-mail: [São Carlos Institute of Chemistry, University of São Paulo, P.O. Box 780, 13560 − 970, São Carlos, SP (Brazil)


    Several studies have found that the Pt{sub 55} nanocluster adopts a distorted reduced core structure, DRC{sub 55}, in which there are 8–11 atoms in the core and 47–44 atoms in the surface, instead of the compact and high-symmetry icosahedron structure, ICO{sub 55}, with 13 and 42 atoms in the core and surface, respectively. The DRC structure has also been obtained as the putative global minimum configuration (GMC) for the Zn{sub 55} (3d), Cd{sub 55} (4d), and Au{sub 55} (5d) systems. Thus, the DRC{sub 55} structure has been reported only for systems with a large occupation of the d-states, where the effects of the occupation of the valence anti-bonding d-states might play an important role. Can we observe the DRC structure for 55-atom transition-metal systems with non-occupation of the anti-bonding d-states? To address this question, we performed a theoretical investigation of the Y {sub 55}, Zr{sub 55}, Nb{sub 55}, Mo{sub 55}, Tc{sub 55}, and Pt{sub 55} nanoclusters, employing density functional theory calculations. For the putative GMCs, we found that the Y {sub 55} adopts the ICO{sub 55} structure, while Nb{sub 55} and Mo{sub 55} adopt a bulk-like fragment based on the hexagonal close-packed structure and Tc{sub 55} adopts a face-centered cubic fragment; however, Zr{sub 55} adopts a DRC{sub 55} structure, like Zn{sub 55}, Cd{sub 55}, Pt{sub 55}, and Au{sub 55}. Thus we can conclude that the preference for DRC{sub 55} structure is not related to the occupation of the anti-bonding d-states, but to a different effect, in fact, a combination of structural and electronic effects. Furthermore, we obtained that the binding energy per atom follows the occupation of the bonding and anti-bonding model, i.e., the stability of the studied systems increases from Y to Tc with a small oscillation for Mo, which also explains the equilibrium bond lengths. We obtained a larger magnetic moment for Y {sub 55} (31 μ{sub B}) which can be explained by the localization of the d

  8. Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy)(2)](2+)

    DEFF Research Database (Denmark)

    Vanko, Gyoergy; Bordage, Amelie; Pápai, Mátyás Imre


    Theoretical predictions show that depending on the populations of the Fe 3d(xy), 3d(xz), and 3d(yz) orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)(2)](2+). The differences in the structure and molecular properties of these B-5...... for the description of the low-spin (LS)-high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations....

  9. Theoretical Issues

    Energy Technology Data Exchange (ETDEWEB)

    Marc Vanderhaeghen


    The theoretical issues in the interpretation of the precision measurements of the nucleon-to-Delta transition by means of electromagnetic probes are highlighted. The results of these measurements are confronted with the state-of-the-art calculations based on chiral effective-field theories (EFT), lattice QCD, large-Nc relations, perturbative QCD, and QCD-inspired models. The link of the nucleon-to-Delta form factors to generalized parton distributions (GPDs) is also discussed.

  10. Instrumentation: Ion Chromatography. (United States)

    Fritz, James S.


    Discusses the importance of ion chromatography in separating and measuring anions. The principles of ion exchange are presented, along with some applications of ion chromatography in industry. Ion chromatography systems are described, as well as ion pair and ion exclusion chromatography, column packings, detectors, and programming. (TW)

  11. Phenolic Compounds of Pinus brutia Ten.: Chemical Investigation and Quantitative Analysis Using an Ultra-Performance Liquid Chromatography Tandem Mass Spectrometry with Electrospray Ionization Source

    Directory of Open Access Journals (Sweden)

    İbrahim Kıvrak


    Full Text Available In this study, phenolic content of Pinus brutia ’s bark was examined using an ultra-performance liquid chromatography tandem mass spectrometry with electrospray ionization source (UPLC-ESI-MS/MS working in multiple reaction monitoring mode. U ltrasonic extraction method with 50% ethanol solution was used for the extraction of bark. The bark of Pinus brutia consisted of 15 compounds: gallic acid, gentisic acid, protocatechuic acid, 4-hydroxy benzoic acid, catechin hydrate, vanillic acid, caffeic acid, vanillin, p-coumaric acid, ferulic acid, myricetin, resveratrol, luteolin, naringenin, kaempferol. Major compound detected was catechin hydrate (28.305 mg 100 g -1 extract. The phenolic compounds of Pinus brutia extract and pycnogenol were compared, and it is shown that both of them consisted of considerable amount of phenolic compounds.

  12. Investigation of the response of wood-rotting fungi to copper stress by size-exclusion chromatography and capillary zone electrophoresis with ICP MS detection

    Energy Technology Data Exchange (ETDEWEB)

    Vacchina, V.; Szpunar, J. [Group of Bio-inorganic Analytical Chemistry, CNRS UMR 5034, Pau (France); Baldrian, P.; Gabriel, J. [Laboratory of the Biochemistry of the Wood-Rotting Fungi, Institute of Microbiology ASCR, Prague (Czech Republic)


    A method based on the coupling of size-exclusion chromatography (SEC) with inductively coupled plasma mass spectrometry (ICP MS) was developed for screening the changes in the bioligand composition of wood-rotting fungi as a function of their exposure to copper stress. Strains of four different species of wood-rotting fungi: Phanerochaete chrysosporium, Schizophyllum commune, Daedalea quercina and Pleurotus ostreatus were examined. Only one, namely Ph. chrysosporium, showed any significant difference in terms of the fingerprint of Cu-binding ligands between control and exposed cells which suggest trapping of Cu(II) by cell walls as the only resistance mechanisms. In the case of Ph. chrysosporium the bioinduction of a new Cu-binding ligand was demonstrated. The presence of a new compound in the SE chromatographic fraction of interest was confirmed by CZE-ICP MS. Attempts to identify the new compound by electrospray MS/MS failed because of insufficient sensitivity. (orig.)

  13. Experimental and theoretical investigation of the production of HCl and some metal chlorides in magmatic/hydrothermal systems. Progress report No. 3

    Energy Technology Data Exchange (ETDEWEB)


    The theoretical analysis is given for calculating the composition of the aqueous vapor and the saline brine (hydrosaline liquid) present at run pressure and temperature in the experiment. The mixture of aqueous vapor and brine is homogenized upon quench. The method for calculating the concentration of HCl and NaCl in the coexisting aqueous vapor and brine is shown.

  14. Theoretical geology (United States)

    Mikeš, Daniel


    Theoretical geology Present day geology is mostly empirical of nature. I claim that geology is by nature complex and that the empirical approach is bound to fail. Let's consider the input to be the set of ambient conditions and the output to be the sedimentary rock record. I claim that the output can only be deduced from the input if the relation from input to output be known. The fundamental question is therefore the following: Can one predict the output from the input or can one predict the behaviour of a sedimentary system? If one can, than the empirical/deductive method has changes, if one can't than that method is bound to fail. The fundamental problem to solve is therefore the following: How to predict the behaviour of a sedimentary system? It is interesting to observe that this question is never asked and many a study is conducted by the empirical/deductive method; it seems that the empirical method has been accepted as being appropriate without question. It is, however, easy to argument that a sedimentary system is by nature complex and that several input parameters vary at the same time and that they can create similar output in the rock record. It follows trivially from these first principles that in such a case the deductive solution cannot be unique. At the same time several geological methods depart precisely from the assumption, that one particular variable is the dictator/driver and that the others are constant, even though the data do not support such an assumption. The method of "sequence stratigraphy" is a typical example of such a dogma. It can be easily argued that all the interpretation resulting from a method that is built on uncertain or wrong assumptions is erroneous. Still, this method has survived for many years, nonwithstanding all the critics it has received. This is just one example of the present day geological world and is not unique. Even the alternative methods criticising sequence stratigraphy actually depart from the same

  15. Theoretical physics

    CERN Document Server

    Joos, Georg


    Among the finest, most comprehensive treatments of theoretical physics ever written, this classic volume comprises a superb introduction to the main branches of the discipline and offers solid grounding for further research in a variety of fields. Students will find no better one-volume coverage of so many essential topics; moreover, since its first publication, the book has been substantially revised and updated with additional material on Bessel functions, spherical harmonics, superconductivity, elastomers, and other subjects.The first four chapters review mathematical topics needed by theo

  16. Theoretical Mathematics (United States)

    Stöltzner, Michael

    Answering to the double-faced influence of string theory on mathematical practice and rigour, the mathematical physicists Arthur Jaffe and Frank Quinn have contemplated the idea that there exists a `theoretical' mathematics (alongside `theoretical' physics) whose basic structures and results still require independent corroboration by mathematical proof. In this paper, I shall take the Jaffe-Quinn debate mainly as a problem of mathematical ontology and analyse it against the backdrop of two philosophical views that are appreciative towards informal mathematical development and conjectural results: Lakatos's methodology of proofs and refutations and John von Neumann's opportunistic reading of Hilbert's axiomatic method. The comparison of both approaches shows that mitigating Lakatos's falsificationism makes his insights about mathematical quasi-ontology more relevant to 20th century mathematics in which new structures are introduced by axiomatisation and not necessarily motivated by informal ancestors. The final section discusses the consequences of string theorists' claim to finality for the theory's mathematical make-up. I argue that ontological reductionism as advocated by particle physicists and the quest for mathematically deeper axioms do not necessarily lead to identical results.

  17. A theoretical investigation of the feasibility of Tannor-Rice type control: Application to selective bond breakage in gas-phase dihalomethanes

    DEFF Research Database (Denmark)

    Shu, Chuan-Cun; Rozgonyi, Tamas; Gonzalez, Leticia;


    Within the math absorption band of CH2BrCl, we theoretically analyze the laser-induced control of the Br/Cl branching ratio, Br + CH2Cl ← CH2BrCl → CH2Br + Cl, with CH2BrCl initially in its vibrational ground state. For weak-field excitation, the Br/Cl branching ratio increases as a function of w...

  18. Application of high-performance anion-exchange chromatography with pulsed amperometric detection and statistical analysis to study oligosaccharide distributions--a complementary method to investigate the structure and some properties of alginates. (United States)

    Ballance, Simon; Holtan, Synnøve; Aarstad, Olav Andreas; Sikorski, Pawel; Skjåk-Braek, Gudmund; Christensen, Bjørn E


    Alginates comprised of essentially alternating units of mannuronic (M) acid-guluronic (G) acid (MG-alginate), and G-blocks isolated from a seaweed where subjected to partial acid hydrolysis at pH 3.5 The chain-length distribution of oligosaccharides in the hydrolysate were investigated by statistical analysis after their separation with high-performance anion-exchange chromatography and pulsed amperometric detection (HPAEC-PAD). Simulated depolymerisation of the MG-alginate provided an estimate of the ratio between two acid hydrolysis rate constants (p=8.3+/-1) and the average distribution of the MM linkages in the original sample of polysaccharide chains. In conclusion, we found HPAEC-PAD together with statistical analysis was a useful method to investigate the fine structure and some properties of binary polysaccharides.

  19. Chemical Investigation of Saponins in Different Parts of Panax notoginseng by Pressurized Liquid Extraction and Liquid Chromatography-Electrospray Ionization-Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Si-Jia Hong


    Full Text Available A pressurized liquid extraction (PLE and high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS method was developed for the qualitative determination of saponins in different parts of P. notoginseng, including rhizome, root, fibre root, seed, stem, leaf and flower. The samples were extracted using PLE. The analysis was achieved on a Zorbax SB-C18 column with gradient elution of acetonitrile and 8 mM aqueous ammonium acetate as mobile phase. The mass spectrometer was operated in the negative ion mode using the electrospray ionization, and a collision induced dissociation (CID experiment was also carried out to aid the identification of compounds. Forty one saponins were identified in different parts of P. notoginseng according to the fragmentation patterns and literature reports, among them, 21 saponins were confirmed by comparing the retention time and ESI-MS data with those of standard compounds. The results showed that the chemical characteristics were obviously diverse in different parts of P. notoginseng, which is helpful for pharmacological evaluation and quality control of P. notoginseng.

  20. Reliable liquid chromatography-mass spectrometry method for investigation of primary aromatic amines migration from food packaging and during industrial curing of multilayer plastic laminates. (United States)

    Lambertini, Francesca; Di Lallo, Valentina; Catellani, Dante; Mattarozzi, Monica; Careri, Maria; Suman, Michele


    Primary aromatic amines (PAAs) can migrate from packaging into food from different sources such as polyurethanic adhesives used for the manufacture of multilayer films, which may contain residual aromatic isocyanates, or recycled paperboard, because of the presence of azo dyes in the printed paper massively used in the recycling process. In the present work, a reliable analytical method, exploiting a conventional high-performance liquid chromatography-(selected ion monitoring)-mass spectrometry system, for PAAs compliance assessment in food contact materials was developed as an effective alternative to the current standard spectrophotometric one, moving in this way from the screening to the accurate and selective quantitation perspective for the analysis of PAAs both in aqueous and acidic food simulants. The main validation parameters were verified achieving very satisfactory results in terms of linearity range, limit of detection (ranging from 0.1 to 1.0 µg kg(-1)) and quantitation (ranging from 0.1 to 3.6 µg kg(-1)), repeatability and accuracy. Suitability of the method was demonstrated for a wide range of commercial samples, chosen among different producers of the most common used food packaging plastic and paperboard categories and then analyzed to assess the risk related to PAAs migration. Finally, the method was also successfully exploited to monitor the evolution of potential PAAs migration during the industrial curing process of multilayer plastic laminates, prior to their release for delivery to the food industry end user.

  1. Effect of parallel segmented flow chromatography on the height equivalent to a theoretical plate III--influence of the column length, particle diameter, and the molecular weight of the analyte on the efficiency gain. (United States)

    Gritti, Fabrice; Pynt, Jarrod; Soliven, Arianne; Dennis, Gary R; Shalliker, R Andrew; Guiochon, Georges


    The effects of column length on performance in segmented flow chromatography were tested. Column efficiencies were measured for 4.6mm I.D. 3, 5, 7.5 and 10 cm long columns packed with 3.0 μm Hypurity-C18 fully porous particles and of 4.6mm I.D. 5, 10, 15 and 25 cm long columns packed with 5 μm Hypersil GOLD C18 particles. For each column length and particle type, two different configurations were tested: (1) both the inlet and outlet column endfittings were standard and (2) the inlet endfitting was standard but the outlet endfitting allowed parallel segmentation of the exiting flow into a central and a peripheral coaxial region. The segmentation flow ratio was set at 45% (for 3 μm) and at 43% or 21% (for 5 μm). Four samples were used, naphthalene, toluene, butylbenzene, and insulin, which has a ten times smaller diffusion coefficient than the small molecules. The column performance for the low molecular weight compound is significantly improved at velocities above the optimum value when the outlet flow rate is segmented because longitudinal diffusion and mass transfer resistance of this compound in the stationary phase are negligible sources of band broadening at reduced linear velocities between 5 and 25. At high flow rate (4 mL/min), the long-range eddy dispersion terms are about 3.9, 3.2, 2.6, and 1.8h unit lower for the 3, 5, 7.5 and 10 cm long columns, respectively. The longer the column, the lower the efficiency improvement because the border effects are smaller. This result was not systematically observed for the columns packed with 5 μm particles because the transverse dispersion is larger. In contrast, the gain in column efficiency is marginal for insulin because the mass transfer mechanism of this compound is mostly controlled by the slow diffusivity of insulin across Hypurity-C18 particles.

  2. Final report for the year 2001 on experimental and theoretical investigations of irradiation effects on physical and mechanical properties of iron and RAFM steels

    DEFF Research Database (Denmark)

    Singh, Bachu Narain


    Effects of neutron irradiation on defect accumulation and physical and mechanical properties have been studied both experimentally and theoretically. Specimens of pure iron and RAFM (reduced activation ferritic-martensic) steels were irradiated todifferent dose levels and at different irradiation...... hardening and formation of “cleared channels” were studied using different computational techniques. Experiments have shown that nano-voids areformed both in pure iron and F82H steel already at 50°C. In pure iron, the formation of nano-voids is detected already at a dose level of ~10-3 dpa. Also in iron...

  3. Interactions fulvate-metal (Zn²⁺, Cu²⁺ and Fe²⁺): theoretical investigation of thermodynamic, structural and spectroscopic properties. (United States)

    Bertoli, Alexandre C; Garcia, Jerusa S; Trevisan, Marcello G; Ramalho, Teodorico C; Freitas, Matheus P


    The use of theoretical calculation to determine structural properties of fulvate-metal complex (zinc, copper and iron) is here related. The species were proposed in the ratio 1:1 and 2:1 for which the molecular structure was obtained through the semi-empirical method PM6. The calculation of thermodynamic stability ([Formula: see text]) predicted that the iron complex were more exo-energetic. Metallic ions were coordinated to the phtalate groups of the model-structure of fulvic acid Suwannee River and the calculations of vibrational frequencies suggested that hydrogen bonds may help on the stability of the complex formation.

  4. 一种新型流体动力轴承的理论研究%Theoretical Investigation on a Novel Hydrodynamic Journal Bearing

    Institute of Scientific and Technical Information of China (English)

    路长厚; 陈淑江; 张建川


    To improve the static and dynamic performance of hydrodynamic journal bearings, a novel bearing is developed, which is a cone-shaped hydrodynamic bearing with spiral oil wedges. The major structural feature of this bearing is the three spiral circular recesses on the bearing's surface, leading to improved characteristics. This paper aims to develop a model for design and calculation of the geometric parameters and the oil film thickness, and to provide a theoretical analysis to the static characteristics using a finite element method. Some new features are introduced.

  5. Quantitative monitoring of tamoxifen in human plasma extended to 40 metabolites using liquid-chromatography high-resolution mass spectrometry: new investigation capabilities for clinical pharmacology. (United States)

    Dahmane, Elyes; Boccard, Julien; Csajka, Chantal; Rudaz, Serge; Décosterd, Laurent; Genin, Eric; Duretz, Bénédicte; Bromirski, Maciej; Zaman, Khalil; Testa, Bernard; Rochat, Bertrand


    Liquid-chromatography (LC) high-resolution (HR) mass spectrometry (MS) analysis can record HR full scans, a technique of detection that shows comparable selectivity and sensitivity to ion transitions (SRM) performed with triple-quadrupole (TQ)-MS but that allows de facto determination of "all" ions including drug metabolites. This could be of potential utility in in vivo drug metabolism and pharmacovigilance studies in order to have a more comprehensive insight in drug biotransformation profile differences in patients. This simultaneous quantitative and qualitative (Quan/Qual) approach has been tested with 20 patients chronically treated with tamoxifen (TAM). The absolute quantification of TAM and three metabolites in plasma was realized using HR- and TQ-MS and compared. The same LC-HR-MS analysis allowed the identification and relative quantification of 37 additional TAM metabolites. A number of new metabolites were detected in patients' plasma including metabolites identified as didemethyl-trihydroxy-TAM-glucoside and didemethyl-tetrahydroxy-TAM-glucoside conjugates corresponding to TAM with six and seven biotransformation steps, respectively. Multivariate analysis allowed relevant patterns of metabolites and ratios to be associated with TAM administration and CYP2D6 genotype. Two hydroxylated metabolites, α-OH-TAM and 4'-OH-TAM, were newly identified as putative CYP2D6 substrates. The relative quantification was precise (<20 %), and the semiquantitative estimation suggests that metabolite levels are non-negligible. Metabolites could play an important role in drug toxicity, but their impact on drug-related side effects has been partially neglected due to the tremendous effort needed with previous MS technologies. Using present HR-MS, this situation should evolve with the straightforward determination of drug metabolites, enlarging the possibilities in studying inter- and intra-patients drug metabolism variability and related effects.

  6. Online coupling of high-resolution chromatography with extreme UV photon activation tandem mass spectrometry: Application to the structural investigation of complex glycans by dissociative photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Ropartz, David, E-mail: [INRA, UR1268 Biopolymers Interactions Assemblies F-44316 Nantes (France); Giuliani, Alexandre [Synchrotron SOLEIL, L' Orme des Merisiers, F-91190 Gif-sur-Yvette (France); UAR 1008 CEPIA, INRA, F-44316 Nantes (France); Fanuel, Mathieu [INRA, UR1268 Biopolymers Interactions Assemblies F-44316 Nantes (France); Hervé, Cécile; Czjzek, Mirjam [Sorbonne Universités, Université Pierre et Marie Curie, Paris VI, CNRS, Integrative Biology of Marine Models, UMR 8227, Station Biologique, Place George Teissier, F29688 Roscoff Cedex (France); Rogniaux, Hélène [INRA, UR1268 Biopolymers Interactions Assemblies F-44316 Nantes (France)


    The activation of ions by extreme-energy photons (XUV) produced by a synchrotron radiation beamline is a powerful method for characterizing complex glycans using tandem mass spectrometry (MS). As previously described, this activation method leads to rich fragmentation spectra with many structurally valuable cross-ring cleavages while maintaining labile modifications on the glycan structures. However, until now, the tandem MS event was too long to be compatible with liquid chromatography elution times. In this work, the duty cycle of the activation and detection of fragments was shortened, and the background signal on the spectra was drastically reduced. Both improvements allowed, for the first time, the successful coupling of a UHPLC system to XUV-activated tandem MS. The approach was used to characterize a complex mixture of oligo-porphyrans, which are a class of highly sulfated oligosaccharides, in a fully automated way. Due to an enhanced dynamic range and an increased sensitivity, some hypothetical structures of low abundance have been unequivocally confirmed in this study and others have been revised. Some previously undescribed species of oligo-porphyrans that exhibit lateral branching have been fully resolved. This work contributes to the scarce knowledge of the structure of porphyrans in red algae and pushes the current capacities of XUV-activation tandem MS by demonstrating the possibility of a direct coupling with UHPLC. This study will considerably broaden the applicability and practicality of this method in many fields of analytical biology. - Highlights: • For the first time, XUV photon activation tandem MS was coupled to UHPLC. • The approach was used to characterize a complex mixture of biomolecules. • The MSMS duty cycle was compatible with elution times of UHPLC without compromised. • Minor species were characterized with an enhanced sensitivity and dynamic range. • These results broaden the application of the technique in many field of

  7. Ceramide lipids in alive and thermally stressed mussels: an investigation by hydrophilic interaction liquid chromatography-electrospray ionization Fourier transform mass spectrometry. (United States)

    Facchini, Laura; Losito, Ilario; Cataldi, Tommaso R I; Palmisano, Francesco


    Hydrophilic interaction liquid chromatography coupled to electrospray ionization-Fourier transform mass spectrometry was employed to study ceramide lipids occurring in mussels of sp. Mytilus galloprovincialis. Lipid extracts from alive mussels and mussels deliberately subjected to specific thermal treatments were analyzed. In particular, single and tandem MS measurements were performed on a hybrid quadrupole-Orbitrap mass spectrometer and then complemented by MS(n) analyses (n = 2, 3) achieved by a linear ion trap mass spectrometer. This approach enabled the characterization of 66 ceramide lipids, encompassing ceramide phosphoethanolamines (CPE), ceramide aminoethylphosphonates (CAEP) and N-monomethylated CAEP. The sphingoid and acyl chains of each ceramide lipid could be distinctly recognized in terms of numbers of carbon atoms and C=C bonds, and indications on the possible location of the latter on the sphingoid chain could be often inferred from fragmentation patterns. The occurrence of several species hydroxylated on the α carbon of the acyl chain was also discovered. On the other hand, the sphingoid chain of ceramide lipids was never found to be involved in oxidation processes, unless forced exposure of the mussel lipid extracts to atmospheric oxygen was performed. CPE(d19:3/16:0) and its hydroxylated form, CPE(d19:3/2-OH-16:0), were found to be the prevailing species among CPE, whereas CAEP(d18:2/16:0), CAEP(d19:3/16:0) and CAEP(d19:3/2-OH-16:0) were the most abundant CAEP. Finally, ceramide lipids showed a remarkably higher stability, compared with glycerophospholipids, in mussels subjected to different thermal treatments. This finding opens interesting perspectives on the role of ceramide-based lipids in the adaptation of aquatic organisms to thermal stresses. Copyright © 2016 John Wiley & Sons, Ltd.

  8. Investigations on the emission of fragrance allergens from scented toys by means of headspace solid-phase microextraction gas chromatography-mass spectrometry. (United States)

    Masuck, Ines; Hutzler, Christoph; Luch, Andreas


    In the revised European toy safety directive 2009/48/EC the application of fragrance allergens in children's toys is restricted. The focus of the present work lies on the instrumental analytics of 13 banned fragrance allergens, as well as on 11 fragrance allergens that require declaration when concentrations surpass 100 microg per gram material. Applying a mixture of ethyl acetate and toluene solid/liquid extraction was performed prior to quantitative analysis of mass contents of fragrances in scented toys. In addition, an easy-to-perform method for the determination of emitted fragrances at 23 degrees C (handling conditions) or at 40 degrees C (worst case scenario) has been worked out to allow for the evaluation of potential risks originating from inhalation of these compounds during handling of or playing with toys. For this purpose a headspace solid-phase microextraction (HS-SPME) technique was developed and coupled to subsequent gas chromatography-mass spectrometry (GC-MS) analysis. Fragrance allergens were adsorbed (extracted) from the gas phase onto an 85 microm polyacrylate fiber while incubating pieces of the scented toys in sealed headspace vials at 23 degrees C and 40 degrees C. Quantification of compounds was performed via external calibration. The newly developed headspace method was subsequently applied to five perfumed toys. As expected, the emission of fragrance allergens from scented toys depends on the temperature and on the content of fragrance allergens present in those samples. In particular at conditions mimicking worst case (40 degrees C), fragrance allergens in toys may pose a risk to children since considerable amounts of compound might be absorbed by lung tissue via breathing of contaminated air.

  9. The role of clinical experience, diagnosis, and theoretical orientation in the treatment of posttraumatic and dissociative disorders: A vignette and survey investigation. (United States)

    Dorahy, Martin J; Lewis-Fernández, Roberto; Krüger, Christa; Brand, Bethany L; Şar, Vedat; Ewing, Jan; Martínez-Taboas, Alfonso; Stavropoulos, Pam; Middleton, Warwick


    Controversy exists regarding the merits of exposure-based treatments for posttraumatic stress disorder (PTSD) versus a phased approach when prominent dissociative symptoms are present. The first aim of this study was to examine the degree to which diagnosing dissociation in two traumatized patients' vignettes influenced clinicians' preference for phase-oriented treatment and whether clinicians' treatment experience contributed to their treatment preference. The second aim was to assess the extent to which participants had observed traumatized patients worsen when treated with exposure therapy or phase-oriented therapy and whether the theoretical orientation and treatment experience of the clinician were related to the observed deterioration. In the tradition of expert and practitioner surveys, 263 clinicians completed a survey of their diagnoses and treatment preferences for two vignettes and their treatment experience, theoretical orientation, and observations of patients' deterioration. When a marked degree of dissociation was noted in the PTSD vignette, respondents favored phased approaches regardless of the diagnosis given. Reports of having observed patient deterioration during both exposure and phased therapy were predicted by years of experience. Psychodynamic therapists reported more observations of worsening during exposure therapy than cognitive behavior therapy therapists. Clinical experience treating PTSD may heighten awareness of negative therapeutic effects, potentially because experienced clinicians have a lower threshold for detecting such effects and because they are referred more challenging cases.

  10. Basic Principles of Chromatography (United States)

    Ismail, Baraem; Nielsen, S. Suzanne

    Chromatography has a great impact on all areas of analysis and, therefore, on the progress of science in general. Chromatography differs from other methods of separation in that a wide variety of materials, equipment, and techniques can be used. [Readers are referred to references (1-19) for general and specific information on chromatography.]. This chapter will focus on the principles of chromatography, mainly liquid chromatography (LC). Detailed principles and applications of gas chromatography (GC) will be discussed in Chap. 29. In view of its widespread use and applications, high-performance liquid chromatography (HPLC) will be discussed in a separate chapter (Chap. 28). The general principles of extraction are first described as a basis for understanding chromatography.

  11. Theoretical Physics 1. Theoretical Mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Dreizler, Reiner M.; Luedde, Cora S. [Frankfurt Univ. (Germany). Inst. fuer Theoretische Physik


    After an introduction to basic concepts of mechanics more advanced topics build the major part of this book. Interspersed is a discussion of selected problems of motion. This is followed by a concise treatment of the Lagrangian and the Hamiltonian formulation of mechanics, as well as a brief excursion on chaotic motion. The last chapter deals with applications of the Lagrangian formulation to specific systems (coupled oscillators, rotating coordinate systems, rigid bodies). The level of this textbook is advanced undergraduate. The authors combine teaching experience of more than 40 years in all fields of Theoretical Physics and related mathematical disciplines and thorough knowledge in creating advanced eLearning content. The text is accompanied by an extensive collection of online material, in which the possibilities of the electronic medium are fully exploited, e.g. in the form of applets, 2D- and 3D-animations. (orig.)

  12. Theoretical Writing

    Directory of Open Access Journals (Sweden)

    Barney G. Glaser, Ph.D., Hon. Ph.D.


    Full Text Available Theoretical sorting has brought the analyst to the point of pent-up pressure to write: to see the months of work actualized in a “piece.” But this is only a personal pressure. The goal of grounded theory methodology, above all is to offer the results to the public, usually through one or more publications. We will focus on writing for publication, which is the most frequent way that the analyst can tell how people are “buying” what really matters in sociology, or in other fields.Both feedback on and use of publications will be the best evaluation of the analyst’s grounded theory. It will be his main source or criticism, constructive critique, and frequently of career rewards. In any case, he has to write to expand his audience beyond the limited number of close colleagues and students. Unless there is a publication, his work will be relegated to limited discussion, classroom presentation, or even private fantasy. The rigor and value of grounded theory work deserves publication. And many analysts have a stake in effecting wider publics, which makes their substantive grounded theory count.

  13. Theoretical geodesy

    Directory of Open Access Journals (Sweden)

    Borkowski Andrzej


    Full Text Available The paper presents a summary of research activities concerning theoretical geodesy performed in Poland in the period of 2011-2014. It contains the results of research on new methods of the parameter estimation, a study on robustness properties of the M-estimation, control network and deformation analysis, and geodetic time series analysis. The main achievements in the geodetic parameter estimation involve a new model of the M-estimation with probabilistic models of geodetic observations, a new Shift-Msplit estimation, which allows to estimate a vector of parameter differences and the Shift-Msplit(+ that is a generalisation of Shift-Msplit estimation if the design matrix A of a functional model has not a full column rank. The new algorithms of the coordinates conversion between the Cartesian and geodetic coordinates, both on the rotational and triaxial ellipsoid can be mentioned as a highlights of the research of the last four years. New parameter estimation models developed have been adopted and successfully applied to the control network and deformation analysis.

  14. Theoretical geodesy (United States)

    Borkowski, Andrzej; Kosek, Wiesław


    The paper presents a summary of research activities concerning theoretical geodesy performed in Poland in the period of 2011-2014. It contains the results of research on new methods of the parameter estimation, a study on robustness properties of the M-estimation, control network and deformation analysis, and geodetic time series analysis. The main achievements in the geodetic parameter estimation involve a new model of the M-estimation with probabilistic models of geodetic observations, a new Shift-Msplit estimation, which allows to estimate a vector of parameter differences and the Shift-Msplit(+) that is a generalisation of Shift-Msplit estimation if the design matrix A of a functional model has not a full column rank. The new algorithms of the coordinates conversion between the Cartesian and geodetic coordinates, both on the rotational and triaxial ellipsoid can be mentioned as a highlights of the research of the last four years. New parameter estimation models developed have been adopted and successfully applied to the control network and deformation analysis. New algorithms based on the wavelet, Fourier and Hilbert transforms were applied to find time-frequency characteristics of geodetic and geophysical time series as well as time-frequency relations between them. Statistical properties of these time series are also presented using different statistical tests as well as 2nd, 3rd and 4th moments about the mean. The new forecasts methods are presented which enable prediction of the considered time series in different frequency bands.

  15. A purge and trap technique to capture volatile compounds combined with comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry to investigate the effect of sulfur-fumigation on Radix Angelicae Dahuricae. (United States)

    Cao, Gang; Li, Qinglin; Zhang, Jida; Cai, Hao; Cai, Baochang


    Sulfur-fumigation is known to reduce volatile compounds that are the main active components in herbs used in herbal medicine. We investigated changes in chemical composition between sun-dried and sulfur-fumigated Radix Angelicae Dahuricae using a purge and trap technique to capture volatile compounds, and two-dimensional gas chromatography/time-of-flight mass spectrometry for identification. Using sun-dried Radix Angelicae Dahuricae samples as a reference, the results showed that 73 volatile compounds, including 12 sulfide compounds, were found to be present only in sulfur-fumigated samples. Furthermore, 32 volatile compounds that were found in sun-dried Radix Angelicae Dahuricae samples disappeared after sulfur-fumigation. The proposed method can be applied to accurately discriminate sulfur-fumigated Radix Angelicae Dahuricae from different commercial sources.

  16. Investigation of an experimental ejector refrigeration machine operating with refrigerant R245fa at design and off-design working conditions. Part 1. Theoretical analysis

    KAUST Repository

    Shestopalov, K.O.


    © 2015 Elsevier Ltd and IIR.All rights reserved. The ejector refrigeration machine (ERM) offers several advantages over other heat-driven refrigeration machine, including simplicity in design and operation, high reliability and low installation cost, which enable its wide application in the production of cooling. In this paper the theoretical analysis of ejector design and ejector refrigeration cycle performance is presented. It is shown that ERM performance characteristics depend strongly on the operating conditions, the efficiency of the ejector used, and the thermodynamic properties of the refrigerant used. A 1-D model for the prediction of the entrainment ratio ω, and an optimal design for ejectors with cylindrical and conical-cylindrical mixing chambers are presented in this paper. In order to increase ERM performance values, it is necessary first of all to improve the performance of the ejector.

  17. Effects of pH value on growth morphology of LaPO{sub 4} nanocrystals: investigated from experiment and theoretical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoyan; Zhang, Zhongju [Ocean University of China, College of Chemistry and Chemical Engineering, Qingdao (China); Zhang, Luo; Wang, Xin [Ocean University of China, Institute of Material Science and Engineering, Qingdao (China)


    The morphologies of the materials have strong effects on their performance in particular applications. In our experiment, we synthesized LaPO{sub 4} successfully by the typical hydrothermal method in acidic conditions. The morphologies, preferred orientation and crystal facets are characterized by scanning electron microscopy, selected-area electron diffraction and high-resolution transmission electron microscopy. Combining the experimental findings, the surface energies of two major surfaces, (110) and (031) planes, were calculated using density functional theory methods. The theoretical calculations on the slabs surface energies were performed to simulate the shape of nanoparticles by the Wulff construction. The experimental results indicate that LaPO{sub 4} prepared in this work shows rodlike structure. The equilibrium shape of clava with large length-diameter ratio is achieved. With increasing hydrogen ion concentration in solutions, the morphologies present as sticks and their length-diameter ratios tend bigger, which is consistent with experimental results to a great extent. (orig.)

  18. Summary of theoretical and experimental investigation of grating type, silicon photovoltaic cells. [using p-n junctions on light receiving surface of base crystal (United States)

    Chen, L. Y.; Loferski, J. J.


    Theoretical and experimental aspects are summarized for single crystal, silicon photovoltaic devices made by forming a grating pattern of p/n junctions on the light receiving surface of the base crystal. Based on the general semiconductor equations, a mathematical description is presented for the photovoltaic properties of such grating-like structures in a two dimensional form. The resulting second order elliptical equation is solved by computer modeling to give solutions for various, reasonable, initial values of bulk resistivity, excess carrier concentration, and surface recombination velocity. The validity of the computer model is established by comparison with p/n devices produced by alloying an aluminum grating pattern into the surface of n-type silicon wafers. Current voltage characteristics and spectral response curves are presented for cells of this type constructed on wafers of different resistivities and orientations.

  19. Joint theoretical experimental investigation of the electron spin resonance spectra of nitroxyl radicals: application to intermediates in in situ nitroxide mediated polymerization (in situ NMP) of vinyl monomers. (United States)

    Zarycz, Natalia; Botek, Edith; Champagne, Benoît; Sciannaméa, Valérie; Jérôme, Christine; Detrembleur, Christophe


    Density functional theory (DFT) calculations have been performed to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated hyperfine coupling constants (HFCCs) to experimental data for a set of linear and cyclic alkylnitroxyl radicals. Considering this tested approach, the nature of different nitroxides has been predicted or confirmed for (a) the reaction of C-phenyl- N- tert-butylnitrone and AIBN, (b) N- tert-butyl-alpha-isopropylnitrone and benzoyl peroxide, (c) tert-butyl methacrylate polymerization in the presence of sodium nitrite as mediator, and (d) for the reaction of a nitroso compound with AIBN. Values of HFCC experimentally determined have been confirmed by DFT calculations.

  20. Theoretical Mechanics Theoretical Physics 1

    CERN Document Server

    Dreizler, Reiner M


    After an introduction to basic concepts of mechanics more advanced topics build the major part of this book. Interspersed is a discussion of selected problems of motion. This is followed by a concise treatment of the Lagrangian and the Hamiltonian formulation of mechanics, as well as a brief excursion on chaotic motion. The last chapter deals with applications of the Lagrangian formulation to specific systems (coupled oscillators, rotating coordinate systems, rigid bodies). The level of this textbook is advanced undergraduate. The authors combine teaching experience of more than 40 years in all fields of Theoretical Physics and related mathematical disciplines and thorough knowledge in creating advanced eLearning content. The text is accompanied by an extensive collection of online material, in which the possibilities of the electronic medium are fully exploited, e.g. in the form of applets, 2D- and 3D-animations. - A collection of 74 problems with detailed step-by-step guidance towards the solutions. - A col...