Recent developments in heavy-ion fusion reactions around the Coulomb barrier

Directory of Open Access Journals (Sweden)

Hagino K.

2016-01-01

Full Text Available The nuclear fusion is a reaction to form a compound nucleus. It plays an important role in several circumstances in nuclear physics as well as in nuclear astrophysics, such as synthesis of superheavy elements and nucleosynthesis in stars. Here we discuss two recent theoretical developments in heavy-ion fusion reactions at energies around the Coulomb barrier. The first topic is a generalization of the Wong formula for fusion cross sections in a single-channel problem. By introducing an energy dependence to the barrier parameters, we show that the generalized formula leads to results practically indistinguishable from a full quantal calculation, even for light symmetric systems such as 12C+12C, for which fusion cross sections show an oscillatory behavior. We then discuss a semi-microscopic modeling of heavy-ion fusion reactions, which combine the coupled-channels approach to the state-of-the-art nuclear structure calculations for low-lying collective motions. We apply this method to subbarrier fusion reactions of 58Ni+58Ni and 40Ca+58Ni systems, and discuss the role of anharmonicity of the low-lying vibrational motions.

DNA nanovehicles and the biological barriers

DEFF Research Database (Denmark)

Okholm, Anders Hauge; Kjems, Jørgen

2016-01-01

DNA is emerging as a smart material to construct nanovehicles for targeted drug delivery. The programmability of Watson-Crick base paring enables construction of defined and dynamic DNA nanostructures of almost arbitrary shape and DNA can readily be functionalized with a variety of molecular...... be overcome. Here, we highlight recent strategies for DNA nanostructures in drug delivery, DNA nanovehicles, to facilitate targeting and crossing of the biological barriers. In light of this, we discuss future solutions and challenges for DNA nanovehicles to unravel their great potential to facilitate...

Effects of breakup of weakly bound projectile and neutron transfer on fusion reactions around Coulomb barrier

International Nuclear Information System (INIS)

Lin, C.J.; Zhang, H.Q.; Yang, F.; Ruan, M.; Liu, Z.H.; Wu, Y.W.; Wu, X.K.; Zhou, P.; Zhang, C.L.; Zhang, G.L.; An, G.P.; Jia, H.M.; Xu, X.X.

2007-01-01

The excitation functions of quasielastic and elastic scattering at backward angles have been measured for the systems of 16 O+ 152 Sm, 6,7 Li+ 208 Pb and 32 S+ 90,96 Zr. The barrier distributions are extracted from these measured excitation functions and compared with the corresponding fusion barrier distributions. Except some details, the barrier distributions derived from the data of fusion and quasielastic/elastic scattering are almost the same for the tightly bound reaction systems. For the reaction systems with weakly bound projectile, the barrier distributions extracted from quasielastic scattering are obviously different from the fusion barrier distributions. However, the barrier distributions extracted from the excitation functions of the quasielastic scattering plus breakup are almost the same as the one extracted from the complete fusion data. This result means that barrier distribution not only bears the information of nuclear structures but also contains the knowledge of reaction mechanisms. Our results show that the complete fusion of the weakly bound projectile with heavy target is suppressed at the above barrier energies as compared with the model predictions. In addition, the measured barrier distribution of 32 S+ 96 Zr is broaden and extends to lower energy than in the case of 32 S+ 90 Zr due to the coupling of neutron transfer with positive Q-values, which result in a significant enhancement of fusion cross sections at the subbarrier energies

Exploring the Possible Use of Information Barriers for future Biological Weapons Verification Regimes

International Nuclear Information System (INIS)

Luke, S.J.

2011-01-01

This report describes a path forward for implementing information barriers in a future generic biological arms-control verification regime. Information barriers have become a staple of discussion in the area of arms control verification approaches for nuclear weapons and components. Information barriers when used with a measurement system allow for the determination that an item has sensitive characteristics without releasing any of the sensitive information. Over the last 15 years the United States (with the Russian Federation) has led on the development of information barriers in the area of the verification of nuclear weapons and nuclear components. The work of the US and the Russian Federation has prompted other states (e.g., UK and Norway) to consider the merits of information barriers for possible verification regimes. In the context of a biological weapons control verification regime, the dual-use nature of the biotechnology will require protection of sensitive information while allowing for the verification of treaty commitments. A major question that has arisen is whether - in a biological weapons verification regime - the presence or absence of a weapon pathogen can be determined without revealing any information about possible sensitive or proprietary information contained in the genetic materials being declared under a verification regime. This study indicates that a verification regime could be constructed using a small number of pathogens that spans the range of known biological weapons agents. Since the number of possible pathogens is small it is possible and prudent to treat these pathogens as analogies to attributes in a nuclear verification regime. This study has determined that there may be some information that needs to be protected in a biological weapons control verification regime. To protect this information, the study concludes that the Lawrence Livermore Microbial Detection Array may be a suitable technology for the detection of the

Exploring the Possible Use of Information Barriers for future Biological Weapons Verification Regimes

Energy Technology Data Exchange (ETDEWEB)

Luke, S J

2011-12-20

This report describes a path forward for implementing information barriers in a future generic biological arms-control verification regime. Information barriers have become a staple of discussion in the area of arms control verification approaches for nuclear weapons and components. Information barriers when used with a measurement system allow for the determination that an item has sensitive characteristics without releasing any of the sensitive information. Over the last 15 years the United States (with the Russian Federation) has led on the development of information barriers in the area of the verification of nuclear weapons and nuclear components. The work of the US and the Russian Federation has prompted other states (e.g., UK and Norway) to consider the merits of information barriers for possible verification regimes. In the context of a biological weapons control verification regime, the dual-use nature of the biotechnology will require protection of sensitive information while allowing for the verification of treaty commitments. A major question that has arisen is whether - in a biological weapons verification regime - the presence or absence of a weapon pathogen can be determined without revealing any information about possible sensitive or proprietary information contained in the genetic materials being declared under a verification regime. This study indicates that a verification regime could be constructed using a small number of pathogens that spans the range of known biological weapons agents. Since the number of possible pathogens is small it is possible and prudent to treat these pathogens as analogies to attributes in a nuclear verification regime. This study has determined that there may be some information that needs to be protected in a biological weapons control verification regime. To protect this information, the study concludes that the Lawrence Livermore Microbial Detection Array may be a suitable technology for the detection of the

Jumping Hurdles: Peptides Able To Overcome Biological Barriers.

Science.gov (United States)

Sánchez-Navarro, Macarena; Teixidó, Meritxell; Giralt, Ernest

2017-08-15

The cell membrane, the gastrointestinal tract, and the blood-brain barrier (BBB) are good examples of biological barriers that define and protect cells and organs. They impose different levels of restriction, but they also share common features. For instance, they all display a high lipophilic character. For this reason, hydrophilic compounds, like peptides, proteins, or nucleic acids have long been considered as unable to bypass them. However, the discovery of cell-penetrating peptides (CPPs) opened a vast field of research. Nowadays, CPPs, homing peptides, and blood-brain barrier peptide shuttles (BBB-shuttles) are good examples of peptides able to target and to cross various biological barriers. CPPs are a group of peptides able to interact with the plasma membrane and enter the cell. They display some common characteristics like positively charged residues, mainly arginines, and amphipathicity. In this field, our group has been focused on the development of proline rich CPPs and in the analysis of the importance of secondary amphipathicity in the internalization process. Proline has a privileged structure being the only amino acid with a secondary amine and a cyclic side chain. These features constrain its structure and hamper the formation of H-bonds. Taking advantage of this privileged structure, three different families of proline-rich peptides have been developed, namely, a proline-rich dendrimer, the sweet arrow peptide (SAP), and a group of foldamers based on γ-peptides. The structure and the mechanism of internalization of all of them has been evaluated and analyzed. BBB-shuttles are peptides able to cross the BBB and to carry with them compounds that cannot reach the brain parenchyma unaided. These peptides take advantage of the natural transport mechanisms present at the BBB, which are divided in active and passive transport mechanisms. On the one hand, we have developed BBB-shuttles that cross the BBB by a passive transport mechanism, like

Electro-induced reactions of biologically important molecules

International Nuclear Information System (INIS)

Kocisek, J.

2010-01-01

The thesis presents the results of research activities in the field of electron interactions with biologically relevant molecules which was carried out during my PhD studies at the Department of Experimental Physics, Comenius University in Bratislava. Electron induced interactions with biologically relevant molecules were experimentally studied using crossed electron-molecule beams experiment. The obtained results, were presented in four publications in international scientific journals. First study of deals with electron impact ionisation of furanose alcohols [see 1. in list of author publications on page 22]. It has been motivated by most important works in the field of electron induced damages of DNA bases [4]. Studied 3-hydroxytetrahydrofuran and tetrahydrofurfuryl alcohol, are important model molecules for more complex biological systems (e.g. deoxyribose).The influence of hydroxyl group on stabilisation of the positive ions of the molecules, together with the stability of furan ring in ionized form are main themes of the study. The studies of small amides and aminoacids are connected to scientific studies in the field of formation of the aminoacids and other biologically relevant molecules in space and works trying to explain electron induced processes in more complex molecules[12, 13, 24]. The most important results were obtained for aminoacid Serine [see 2. in list of author publications on page 22]. We have showed that additional OH group of Serine considerably lower the reaction enthalpy limit of reactions resulting to formation of neutral water molecules, in comparison to other amino acids. Also the study of (M-H)- reaction channel using the electron beam with FWHM under 100 meV is of high importance in the field. The last part of the thesis is focused on the electron interactions with organosilane compounds. Materials prepared from organosilane molecules in plasmas have wide range of applications in both biology and medicine. We have studied electron

Recent experimental results in sub- and near-barrier heavy-ion fusion reactions

Energy Technology Data Exchange (ETDEWEB)

Montagnoli, Giovanna [Dipartimento di Fisica e Astronomia, Universita di Padova (Italy); INFN Sezione di Padova (Italy); Stefanini, Alberto M. [INFN, Laboratori Nazionali di Legnaro, Legnaro (Padova) (Italy)

2017-08-15

Recent advances obtained in the field of near and sub-barrier heavy-ion fusion reactions are reviewed. Emphasis is given to the results obtained in the last decade, and focus is mainly on the experimental work performed concerning the influence of transfer channels on fusion cross sections and the hindrance phenomenon far below the barrier. Indeed, early data of sub-barrier fusion taught us that cross sections may strongly depend on the low-energy collective modes of the colliding nuclei, and, possibly, on couplings to transfer channels. The coupled-channels (CC) model has been quite successful in the interpretation of the experimental evidences. Fusion barrier distributions often yield the fingerprint of the relevant coupled channels. Recent results obtained by using radioactive beams are reported. At deep sub-barrier energies, the slope of the excitation function in a semi-logarithmic plot keeps increasing in many cases and standard CC calculations overpredict the cross sections. This was named a hindrance phenomenon, and its physical origin is still a matter of debate. Recent theoretical developments suggest that this effect, at least partially, may be a consequence of the Pauli exclusion principle. The hindrance may have far-reaching consequences in astrophysics where fusion of light systems determines stellar evolution during the carbon and oxygen burning stages, and yields important information for exotic reactions that take place in the inner crust of accreting neutron stars. (orig.)

Variation in reaction norms: Statistical considerations and biological interpretation.

Science.gov (United States)

Morrissey, Michael B; Liefting, Maartje

2016-09-01

Analysis of reaction norms, the functions by which the phenotype produced by a given genotype depends on the environment, is critical to studying many aspects of phenotypic evolution. Different techniques are available for quantifying different aspects of reaction norm variation. We examine what biological inferences can be drawn from some of the more readily applicable analyses for studying reaction norms. We adopt a strongly biologically motivated view, but draw on statistical theory to highlight strengths and drawbacks of different techniques. In particular, consideration of some formal statistical theory leads to revision of some recently, and forcefully, advocated opinions on reaction norm analysis. We clarify what simple analysis of the slope between mean phenotype in two environments can tell us about reaction norms, explore the conditions under which polynomial regression can provide robust inferences about reaction norm shape, and explore how different existing approaches may be used to draw inferences about variation in reaction norm shape. We show how mixed model-based approaches can provide more robust inferences than more commonly used multistep statistical approaches, and derive new metrics of the relative importance of variation in reaction norm intercepts, slopes, and curvatures. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

Direct mapping of the angle-dependent barrier to reaction for Cl + CHD3 using polarized scattering data

Science.gov (United States)

Pan, Huilin; Wang, Fengyan; Czakó, Gábor; Liu, Kopin

2017-12-01

The transition state, which gates and modulates reactive flux, serves as the central concept in our understanding of activated reactions. The barrier height of the transition state can be estimated from the activation energy taken from thermal kinetics data or from the energetic threshold in the measured excitation function (the dependence of reaction cross-sections on initial collision energies). However, another critical and equally important property, the angle-dependent barrier to reaction, has not yet been amenable to experimental determination until now. Here, using the benchmark reaction of Cl + CHD3(v1 = 1) as an example, we show how to map this anisotropic property of the transition state as a function of collision energy from the preferred reactant bond alignment of the backward-scattered products—the imprints of small impact-parameter collisions. The deduced bend potential at the transition state agrees with ab initio calculations. We expect that the method should be applicable to many other direct reactions with a collinear barrier.

Parabolic equations in biology growth, reaction, movement and diffusion

CERN Document Server

Perthame, Benoît

2015-01-01

This book presents several fundamental questions in mathematical biology such as Turing instability, pattern formation, reaction-diffusion systems, invasion waves and Fokker-Planck equations. These are classical modeling tools for mathematical biology with applications to ecology and population dynamics, the neurosciences, enzymatic reactions, chemotaxis, invasion waves etc. The book presents these aspects from a mathematical perspective, with the aim of identifying those qualitative properties of the models that are relevant for biological applications. To do so, it uncovers the mechanisms at work behind Turing instability, pattern formation and invasion waves. This involves several mathematical tools, such as stability and instability analysis, blow-up in finite time, asymptotic methods and relative entropy properties. Given the content presented, the book is well suited as a textbook for master-level coursework.

A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

International Nuclear Information System (INIS)

Alves, Giselle M; Kremer, Gilberto M; Marques, Wilson Jr; Soares, Ana Jacinta

2011-01-01

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman–Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal–diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode

A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

Science.gov (United States)

Alves, Giselle M.; Kremer, Gilberto M.; Marques, Wilson, Jr.; Jacinta Soares, Ana

2011-03-01

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

Complete and incomplete fusion dynamics of {sup 6,7}Li + {sup 159}Tb reactions near the Coulomb barrier

Energy Technology Data Exchange (ETDEWEB)

Gautam, Manjeet Singh [Thapar University, School of Physics and Materials Science, Patiala (India); Indus Degree College, Department of Physics, Kinana, Jind, Haryana (India); Grover, Neha; Sharma, Manoj K. [Thapar University, School of Physics and Materials Science, Patiala (India)

2017-01-15

The complete fusion (CF) and incomplete fusion (ICF) cross-sections are estimated for {sup 6,} {sup 7}Li + {sup 159}Tb reactions using the energy-dependent Woods-Saxon potential model (EDWSP model) and dynamical cluster-decay model (DCM). The CF data of the {sup 6}Li + {sup 159}Tb({sup 7}Li + {sup 159}Tb) reaction at above barrier energies is suppressed with reference to expectations of the EDWSP model by 25% (20%) which is smaller than the reported data by ∝ 9% (6%). This suppression is correlated with the projectile breakup effect. The projectiles {sup 6,7}Li are loosely bound systems, which may break up into charged fragments prior to reaching the fusion barrier and subsequently one of the fragment is captured by the target leading to the suppression of fusion data at above barrier energies. The sum of CF and ICF, which is termed as total fusion cross-section (TF), removes the discrepancies between theoretical predictions and the above barrier complete fusion data and hence is adequately explained via the EDWSP model over a wide range of energy spread across the Coulomb barrier. In addition to fusion, the decay mechanism of {sup 6}Li + {sup 159}Tb reaction is studied within the framework of the dynamical cluster-decay model (DCM). The breakup of the projectile ({sup 6}Li) in the entrance channel indicates the presence of ICF, which is investigated further using the collective clusterization approach of DCM. The present theoretical analysis suggests that a larger barrier modification is needed to address the fusion data of chosen reactions in the below barrier energy region. (orig.)

Quasi-elastic scattering an alternative tool for mapping the fusion barriers for heavy-ion induced fusion reaction

International Nuclear Information System (INIS)

Behera, B.R.

2016-01-01

Heavy element synthesis through heavy-ion induced fusion reaction is an active field in contemporary nuclear physics. Exact knowledge of fusion barrier is one of the essential parameters for planning any experiments for heavy element production. Theoretically there are many models available to predict the exact barrier. Though these models are successful for predicting the fusion of medium mass nuclei, it somehow fails for predicting the exact location of barrier for fusion of heavy nuclei. Experimental determination of barrier for such reactions is required for future experiments for the synthesis of heavy elements. Traditionally fusion barrier is determined taking a double derivative of fusion excitation function. However, such method is difficult in case of fusion of heavy nuclei due to its very low fusion/capture cross section and its experimental complications. Alternatively fusion barrier can be determined by measuring the quasi-elastic cross section at backward angles. This method can be applied for determining the fusion barrier for the fusion of heavy nuclei. Experimental determination of fusion barrier by different methods and comparison of the fusion excitation function and quasi-elastic scattering methods for the determination of fusion barrier are reviewed. At IUAC, New Delhi recently a program has been started for the measurement of fusion barrier through quasi-elastic scattering methods. The experimental facility and the first results of the experiments carried out with this facility are presented. (author)

Sub-barrier quasifission in heavy element formation reactions with deformed actinide target nuclei

Science.gov (United States)

Hinde, D. J.; Jeung, D. Y.; Prasad, E.; Wakhle, A.; Dasgupta, M.; Evers, M.; Luong, D. H.; du Rietz, R.; Simenel, C.; Simpson, E. C.; Williams, E.

2018-02-01

Background: The formation of superheavy elements (SHEs) by fusion of two massive nuclei is severely inhibited by the competing quasifission process. Low excitation energies favor SHE survival against fusion-fission competition. In "cold" fusion with spherical target nuclei near 208Pb, SHE yields are largest at beam energies significantly below the average capture barrier. In "hot" fusion with statically deformed actinide nuclei, this is not the case. Here the elongated deformation-aligned configurations in sub-barrier capture reactions inhibits fusion (formation of a compact compound nucleus), instead favoring rapid reseparation through quasifission. Purpose: To determine the probabilities of fast and slow quasifission in reactions with prolate statically deformed actinide nuclei, through measurement and quantitative analysis of the dependence of quasifission characteristics at beam energies spanning the average capture barrier energy. Methods: The Australian National University Heavy Ion Accelerator Facility and CUBE fission spectrometer have been used to measure fission and quasifission mass and angle distributions for reactions with projectiles from C to S, bombarding Th and U target nuclei. Results: Mass-asymmetric quasifission occurring on a fast time scale, associated with collisions with the tips of the prolate actinide nuclei, shows a rapid increase in probability with increasing projectile charge, the transition being centered around projectile atomic number ZP=14 . For mass-symmetric fission events, deviations of angular anisotropies from expectations for fusion fission, indicating a component of slower quasifission, suggest a similar transition, but centered around ZP˜8 . Conclusions: Collisions with the tips of statically deformed prolate actinide nuclei show evidence for two distinct quasifission processes of different time scales. Their probabilities both increase rapidly with the projectile charge. The probability of fusion can be severely

Organometallic copper I, II or III species in an intramolecular dechlorination reaction

KAUST Repository

Poater, Albert; Cavallo, Luigi

2013-01-01

these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction

H + H2 reaction barrier: A fixed-node quantum Monte Carlo study

International Nuclear Information System (INIS)

Barnett, R.N.; Reynolds, P.J.; Lester, W.A. Jr.

1985-01-01

The classical barrier height for the H+H 2 exchange reaction, as well as the energies at two other points along the reaction path, are calculated using fixed-node quantum Monte Carlo (FNQMC). Several single-determinant importance functions are used at the saddle point in order to relate the quality of the importance function to the accuracy and precision of the final result. The computed barrier is an upper bound since the energy of H and of H 2 is obtained exactly by FNQMC. Our best upper bound (9.70 +- 0.13 kcal/mol) has a mean within 0.1 kcal/mol of the presumed exact value. This best bound is obtained with a single determinant, double-zeta basis importance function. Contrary to experience with expansion methods, it is found that an importance function with a basis set of near Hartree--Fock quality, as well as one derived from a spin-unrestricted SCF calculation, are among the least efficient and least accurate of the importance functions used. Specifically, a nodal surface appearing in the lowest energy molecular orbital in these functions apparently increases the FNQMC energy. The FNQMC energy at the two other points along the reaction path is found to agree with the most accurate CI results of Liu to within statistical error

Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

International Nuclear Information System (INIS)

Santos, Elizabeth; Schmickler, Wolfgang

2008-01-01

A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

Near and sub-barrier reactions of 8B

Directory of Open Access Journals (Sweden)

Kolata J. J.

2017-01-01

Full Text Available Four classes of measurements that are important for achieving a complete understanding of the reactions of exotic nuclei are identified and classified according to their degree of difficulty. Previously reported data for near- and sub-barrier fusion of 8B+58Ni are critically reviewed. The influence of breakup protons on the evaporation proton measurements for this system is shown to be small at all energies except for the lowest one measured, and corrections are made for this process. Model dependencies in the deduced fusion cross sections are assessed using three different evaporation codes. Data sets for targets of 58Ni and 28Si are shown to be consistent with each other, and with fusion enhancement up to energies that are greater than the Coulomb barrier Vb (Ec.m. ≲ Vb + 1.5×ћω. An important difference with the behavior of neutron-halo systems is thereby confirmed. Possible fusion suppression beyond this energy is suggested by the 28Si data. A proposal to measure the 8B+40Ar fusion cross section using an active-target time projection chamber is discussed.

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

Science.gov (United States)

Ahlborg, Nadia L.; Zhu, Dongming

2013-01-01

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Role of transfer reactions in heavy-ion collisions at the Coulomb barrier

Directory of Open Access Journals (Sweden)

Pollarolo Giovanni

2011-10-01

Full Text Available One and two neutron transfer reactions are discussed in the semiclassical formalism. The twoneutrons transfer cross sections are calculated in the successive approximation. Comparisons with new experimental data below the Coulomb barrier are discussed in term of transfer probabilities as a function of the distance of closest approach for Coulomb scattering.

Multi-nucleon transfer: a probe to investigate the reaction mechanism around the barrier

International Nuclear Information System (INIS)

Mandal, Samit K.

2014-01-01

The investigation of multi-nucleon transfer mechanism offers valuable information on the pairing interactions that enhance the transfer of nucleon pairs across heavy ions involved in the reaction. These reactions are also a useful tool to study exotic nuclei far from the stability line, which can be explored with the new generation radioactive beam facility. In this talk, multi-nucleon transfer reaction mechanisms between heavy ions and their effect on the reaction dynamics around the coulomb barrier energies have been discussed. Experimental results will be presented with a semi classical description of multi nucleon transfer reaction calculation. One and two nucleon transfer cross sections reproduced using a quantum mechanical coupled channel calculations will also be discussed. A feasibility of investigation of multi-nucleon transfer mechanism to explore the pairing correlation at moderate spin states with radioactive beams will be discussed. (author)

Towards a barrier height benchmark set for biologically relevant systems.

Science.gov (United States)

Kromann, Jimmy C; Christensen, Anders S; Cui, Qiang; Jensen, Jan H

2016-01-01

We have collected computed barrier heights and reaction energies (and associated model structures) for five enzymes from studies published by Himo and co-workers. Using this data, obtained at the B3LYP/6- 311+G(2d,2p)[LANL2DZ]//B3LYP/6-31G(d,p) level of theory, we then benchmark PM6, PM7, PM7-TS, and DFTB3 and discuss the influence of system size, bulk solvation, and geometry re-optimization on the error. The mean absolute differences (MADs) observed for these five enzyme model systems are similar to those observed for PM6 and PM7 for smaller systems (10-15 kcal/mol), while DFTB results in a MAD that is significantly lower (6 kcal/mol). The MADs for PMx and DFTB3 are each dominated by large errors for a single system and if the system is disregarded the MADs fall to 4-5 kcal/mol. Overall, results for the condensed phase are neither more or less accurate relative to B3LYP than those in the gas phase. With the exception of PM7-TS, the MAD for small and large structural models are very similar, with a maximum deviation of 3 kcal/mol for PM6. Geometry optimization with PM6 shows that for one system this method predicts a different mechanism compared to B3LYP/6-31G(d,p). For the remaining systems, geometry optimization of the large structural model increases the MAD relative to single points, by 2.5 and 1.8 kcal/mol for barriers and reaction energies. For the small structural model, the corresponding MADs decrease by 0.4 and 1.2 kcal/mol, respectively. However, despite these small changes, significant changes in the structures are observed for some systems, such as proton transfer and hydrogen bonding rearrangements. The paper represents the first step in the process of creating a benchmark set of barriers computed for systems that are relatively large and representative of enzymatic reactions, a considerable challenge for any one research group but possible through a concerted effort by the community. We end by outlining steps needed to expand and improve the data set

Fusion barrier distributions from capture and quasi-elastic excitation functions measured in reaction 36S, 48Ca, 64Ni+238U

International Nuclear Information System (INIS)

Kozulin, E. M.

2009-01-01

The subbarrier fusion enhancement in reactions with heavy ions were explained by taking into account coupling between relative motion and intrinsic degrees of freedom of interacting nuclei. The coupling of reaction channels manifests itself in the potential barrier between interacting nuclei giving rise to a distribution of fusion barrier instead of single barrier.Capture and quasi-elastic scattering excitation functions at backward angles were measured for 3 6S , 4 8C a, 6 4N i+2 38U reactions systems at energies close and below the Coulomb barrier (i.e. when the influence of the shell effects on the fusion and characteristics of the decay of the composite system is considerable). Representations of the barrier distributions were extracted from both capture and quasi-elastic data. The experimental representations of barrier distributions were compared with coupled-channel calculations using CCFULL code. The major part of these experiments has been performed at the U-400 accelerator of the Flerov Laboratory of Nuclear Reactions (JINR, Dubna); at the TANDEM-ALPI accelerator of the LNL (INFN, Legnaro, Italy) and at the Accelerator Laboratory of University of Jyvaeskylae (JYFL, Finland) using a time-of-flight spectrometer of fission fragments CORSET (CORrelation SET-up.) The extraction of the masses and Total Kinetic Energy (TKE) of the binary reaction products is based upon the analysis of the two-body velocity In the case of the fusion-fission and quasi-fission processes, the observed peculiarities of mass and energy distributions of the fragments, the ratio between the fusion-fission and quasi-fission cross sections are determined deformations of interaction nuclei and angular momentum carried in the di-nuclear system and the shell structure of the formed fragments. In this work, the high-precision capture and quasi-elastic scattering excitation function data are presented.The influence of projectile and target excitations and nucleon transfer on fusion barrier

Breaking the Biological Barriers to Cellulosic Ethanol: A Joint Research Agenda

Energy Technology Data Exchange (ETDEWEB)

Houghton, John [Dept. of Energy (DOE), Washington DC (United States); Weatherwax, Sharlene [Dept. of Energy (DOE), Washington DC (United States); Ferrell, John [Dept. of Energy (DOE), Washington DC (United States)

2006-06-07

The Biomass to Biofuels Workshop, held December 7–9, 2005, was convened by the Department of Energy’s Office of Biological and Environmental Research in the Office of Science; and the Office of the Biomass Program in the Office of Energy Efficiency and Renewable Energy. The purpose was to define barriers and challenges to a rapid expansion of cellulosic-ethanol production and determine ways to speed solutions through concerted application of modern biology tools as part of a joint research agenda. Although the focus was ethanol, the science applies to additional fuels that include biodiesel and other bioproducts or coproducts having critical roles in any deployment scheme.

Many-nucleon transfer reactions at the coulomb barrier

International Nuclear Information System (INIS)

Wegmann, H.

1974-01-01

The aim of the present work was to investigate the many-nucleon transfer with heavy ion radiation near the coulomb barrier. The neutron-rich targets 76 Ge, sup(92,94,96)Zr and 100 Mo were thus irradiated with 32 S and 34 S radiation. By measuring the activity of the back-scattered light reaction products in the transfer, total cross sections were determined for the 3p, 4p, 3pn, 4pn, 3n, 4n and 6n transfer. Excitation functions for the 3p, 4p, 3pn and 4pn transfer were measured for the target-projectile combination 96 Zr- 32 S. Differential cross sections could be determined with 96 Zr and 100 Mo. The results were compared with various theoretical calculations. (orig./LH) [de

Derivatization reactions in the gas—liquid chromatographic analysis of drugs in biological fluids

NARCIS (Netherlands)

Hulshoff, A.; Lingeman, H.

1984-01-01

Alkylation, acylation, silylation and other derivatization reactions applied to the gas chromatographic analysis of drugs in biological matrices are reviewed. Reaction conditions are discussed in relation to reaction mechanisms. Detector-oriented labelling of drugs, and derivatization with chiral

Estimates of fission barrier heights for neutron-deficient Po to Ra nuclei produced in fusion reactions

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Sagaidak Roman

2017-01-01

Full Text Available The cross section data for fission and evaporation residue production in fusion reactions leading to nuclei from Po to Ra have been considered in a systematic way in the framework of the conventional barrier-passing (fusion model coupled with the statistical model. The cross section data obtained in very asymmetric projectile-target combinations can be described within these models rather well with the adjusted model parameters. In particular, one can scale and fix the macroscopic (liquid-drop fission barrier heights (FBHs for nuclei involved in the de-excitation of compound nuclei produced in the reactions. The macroscopic FBHs for nuclei from Po to Ra have been derived in the framework of such analysis and compared with the predictions of various theoretical models.

Biologic Treatments for Sports Injuries II Think Tank-Current Concepts, Future Research, and Barriers to Advancement, Part 1: Biologics Overview, Ligament Injury, Tendinopathy.

Science.gov (United States)

LaPrade, Robert F; Geeslin, Andrew G; Murray, Iain R; Musahl, Volker; Zlotnicki, Jason P; Petrigliano, Frank; Mann, Barton J

2016-12-01

Biologic therapies, including stem cells, platelet-rich plasma, growth factors, and other biologically active adjuncts, have recently received increased attention in the basic science and clinical literature. At the 2015 AOSSM Biologics II Think Tank held in Colorado Springs, Colorado, a group of orthopaedic surgeons, basic scientists, veterinarians, and other investigators gathered to review the state of the science for biologics and barriers to implementation of biologics for the treatment of sports medicine injuries. This series of current concepts reviews reports the summary of the scientific presentations, roundtable discussions, and recommendations from this think tank. © 2016 The Author(s).

Nonlinear reaction-diffusion systems conditional symmetry, exact solutions and their applications in biology

CERN Document Server

Cherniha, Roman

2017-01-01

This book presents several fundamental results in solving nonlinear reaction-diffusion equations and systems using symmetry-based methods. Reaction-diffusion systems are fundamental modeling tools for mathematical biology with applications to ecology, population dynamics, pattern formation, morphogenesis, enzymatic reactions and chemotaxis. The book discusses the properties of nonlinear reaction-diffusion systems, which are relevant for biological applications, from the symmetry point of view, providing rigorous definitions and constructive algorithms to search for conditional symmetry (a nontrivial generalization of the well-known Lie symmetry) of nonlinear reaction-diffusion systems. In order to present applications to population dynamics, it focuses mainly on two- and three-component diffusive Lotka-Volterra systems. While it is primarily a valuable guide for researchers working with reaction-diffusion systems  and those developing the theoretical aspects of conditional symmetry conception,...

Towards a barrier height benchmark set for biologically relevant systems

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Jimmy C. Kromann

2016-05-01

Full Text Available We have collected computed barrier heights and reaction energies (and associated model structures for five enzymes from studies published by Himo and co-workers. Using this data, obtained at the B3LYP/6- 311+G(2d,2p[LANL2DZ]//B3LYP/6-31G(d,p level of theory, we then benchmark PM6, PM7, PM7-TS, and DFTB3 and discuss the influence of system size, bulk solvation, and geometry re-optimization on the error. The mean absolute differences (MADs observed for these five enzyme model systems are similar to those observed for PM6 and PM7 for smaller systems (10–15 kcal/mol, while DFTB results in a MAD that is significantly lower (6 kcal/mol. The MADs for PMx and DFTB3 are each dominated by large errors for a single system and if the system is disregarded the MADs fall to 4–5 kcal/mol. Overall, results for the condensed phase are neither more or less accurate relative to B3LYP than those in the gas phase. With the exception of PM7-TS, the MAD for small and large structural models are very similar, with a maximum deviation of 3 kcal/mol for PM6. Geometry optimization with PM6 shows that for one system this method predicts a different mechanism compared to B3LYP/6-31G(d,p. For the remaining systems, geometry optimization of the large structural model increases the MAD relative to single points, by 2.5 and 1.8 kcal/mol for barriers and reaction energies. For the small structural model, the corresponding MADs decrease by 0.4 and 1.2 kcal/mol, respectively. However, despite these small changes, significant changes in the structures are observed for some systems, such as proton transfer and hydrogen bonding rearrangements. The paper represents the first step in the process of creating a benchmark set of barriers computed for systems that are relatively large and representative of enzymatic reactions, a considerable challenge for any one research group but possible through a concerted effort by the community. We end by outlining steps needed to expand and

Dynamics of {sup 58}Ni + {sup 54}Fe → {sup 112}Xe* reaction across the Coulomb barrier

Energy Technology Data Exchange (ETDEWEB)

Kaur, Manpreet; Sharma, Manoj K. [Thapar University, School of Physics and Materials Science, Patiala (India)

2014-03-15

The dynamical cluster-decay model (DCM) has been applied to study the decay of the {sup 112}Xe* compound nucleus formed in the massive heavy-ion reaction {sup 58}Ni + {sup 54}Fe at energies across the Coulomb barrier with E{sub c.m.} ∼ 85-110 MeV. The calculations are done for spherical fragmentation as well as by including deformation and orientation degrees of freedom of the decaying fragments. DCM-based cross sections give a nice description of the experimental fusion excitation function σ{sub ER}, within one parameter fitting, the neck length parameter (ΔR), whose value remains within the range of nuclear proximity interaction. The barrier height corresponding to the neck length parameter brings into the picture the barrier modification which enables us to address the data particularly at below barrier energies. The role of excitation energy (or temperature), deformations, orientations, angular momentum and diffuseness parameter is investigated to understand the dynamics of the {sup 58}Ni + {sup 54}Fe reaction. Finally the N/Z dependence of the fragmentation structure of different compound systems formed via {sup 58}Ni beam (projectile) is explored. (orig.)

Nucleic Acid Templated Reactions for Chemical Biology.

Science.gov (United States)

Di Pisa, Margherita; Seitz, Oliver

2017-06-21

Nucleic acid directed bioorthogonal reactions offer the fascinating opportunity to unveil and redirect a plethora of intracellular mechanisms. Nano- to picomolar amounts of specific RNA molecules serve as templates and catalyze the selective formation of molecules that 1) exert biological effects, or 2) provide measurable signals for RNA detection. Turnover of reactants on the template is a valuable asset when concentrations of RNA templates are low. The idea is to use RNA-templated reactions to fully control the biodistribution of drugs and to push the detection limits of DNA or RNA analytes to extraordinary sensitivities. Herein we review recent and instructive examples of conditional synthesis or release of compounds for in cellulo protein interference and intracellular nucleic acid imaging. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Beyond mean-field approach to heavy-ion reactions around the Coulomb barrier

Directory of Open Access Journals (Sweden)

Ayik Sakir

2011-10-01

Full Text Available Dissipation and fluctuations of one-body observables in heavy-ion reactions around the Coulomb barrier are investigated with a microscopic stochastic mean-field approach. By projecting the stochastic meanfield dynamics on a suitable collective path, transport coefficients associated with the relative distance between colliding nuclei and a fragment mass are extracted. Although microscopic mean-field approach is know to underestimate the variance of fragment mass distribution, the description of the variance is much improved by the stochastic mean-field method. While fluctuations are consistent with the empirical (semiclassical analysis of the experimental data, concerning mean values of macroscopic variables the semiclassical description breaks down below the Coulomb barrier.

Coupled-channel calculation for cross section of fusion and barrier distribution of {}^{16,17,18}O + {}^{16}O reactions

Science.gov (United States)

Fereidonnejad, R.; Sadeghi, H.; Ghambari, M.

2018-03-01

In this work, the effect of multi-phonon excitation on heavy-ion fusion reactions has been studied and fusion barrier distributions of energy intervals near and below the Coulomb barrier have been studied for 16,17,18O + 16O reactions. The structure and deformation of nuclear projectiles have been studied. Given the adaptation of computations to experimental data, our calculations predict the behavior of reactions in intervals of energy in which experimental measurements are not available. In addition the S-factor for these reactions has been calculated. The results showed that the structure and deformation of a nuclear projectile are important factors. The S-factor, obtained in the coupled-channel calculations for the {}^{16}O + {}^{16}O, {}^{17}O +{}^{16}O and {}^{18}O +{}^{16}O reactions, showed good agreement with the experimental data and had a maximum value at an energy near 5, 4.5 and 4 MeV, respectively.

Nuclear reactions of the system 6 Li on 58 Ni near the Coulomb barrier

International Nuclear Information System (INIS)

Lizcano, D.; Aguilera, E.F.; Garcia M, H.; Martinez Q, E.

2004-01-01

Protons, alpha particles and deuterons coming from the reactions 6 Li + 58 Ni are detected to three different energy around the Coulomb barrier. The possible effects of the weakly bound character of the projectile are studied and the results are compared with previous data for the system 6 Li + 59 Co. (Author)

Fusability and fissionability in 86Kr induced reactions near and below the fusion barrier

International Nuclear Information System (INIS)

Reisdorf, W.; Hessberger, F.P.; Hildenbrand, K.D.; Hofmann, S.; Muenzenberg, G.; Schmidt, K.H.; Schneider, W.F.W.; Suemmerer, K.; Wirth, G.; Kratz, J.V.; Schlitt, K.; Sahm, C.C.

1985-04-01

Evaporation-residue excitation functions for the reactions 86 Kr + sup(70,76)Ge, sup(92,100)Mo, sup(99,102,104)Ru have been measured using activation methods and the velocity filter SHIP. The data span the region from well below the fusion barrier up to and beyond the energy where limitation by fission competition takes place. The data are shown to be compatible with the concept of complete fusion followed by the statistical decay of the equilibrated compound nucleus. Information on both the fusion probability at and below the fusion threshold and the fissionability of the compound nuclei formed is extracted. The model dependence of the extracted fission barriers is discussed in detail. In analogy to studies involving lighter projectiles, strong correlations between the low-energy nuclear-structure properties of the nuclei and the subbarrier fusion probability are found. A relative shift of the fusion barrier to higher energies, that increases with the number of valence neutrons in the target nuclei, is observed. (orig.)

Molecular biology of the blood-brain and the blood-cerebrospinal fluid barriers: similarities and differences

Directory of Open Access Journals (Sweden)

Redzic Zoran

2011-01-01

Full Text Available Abstract Efficient processing of information by the central nervous system (CNS represents an important evolutionary advantage. Thus, homeostatic mechanisms have developed that provide appropriate circumstances for neuronal signaling, including a highly controlled and stable microenvironment. To provide such a milieu for neurons, extracellular fluids of the CNS are separated from the changeable environment of blood at three major interfaces: at the brain capillaries by the blood-brain barrier (BBB, which is localized at the level of the endothelial cells and separates brain interstitial fluid (ISF from blood; at the epithelial layer of four choroid plexuses, the blood-cerebrospinal fluid (CSF barrier (BCSFB, which separates CSF from the CP ISF, and at the arachnoid barrier. The two barriers that represent the largest interface between blood and brain extracellular fluids, the BBB and the BCSFB, prevent the free paracellular diffusion of polar molecules by complex morphological features, including tight junctions (TJs that interconnect the endothelial and epithelial cells, respectively. The first part of this review focuses on the molecular biology of TJs and adherens junctions in the brain capillary endothelial cells and in the CP epithelial cells. However, normal function of the CNS depends on a constant supply of essential molecules, like glucose and amino acids from the blood, exchange of electrolytes between brain extracellular fluids and blood, as well as on efficient removal of metabolic waste products and excess neurotransmitters from the brain ISF. Therefore, a number of specific transport proteins are expressed in brain capillary endothelial cells and CP epithelial cells that provide transport of nutrients and ions into the CNS and removal of waste products and ions from the CSF. The second part of this review concentrates on the molecular biology of various solute carrier (SLC transport proteins at those two barriers and underlines

Zebrafish as a visual and dynamic model to study the transport of nanosized drug delivery systems across the biological barriers.

Science.gov (United States)

Li, Ye; Miao, Xiaoqing; Chen, Tongkai; Yi, Xiang; Wang, Ruibing; Zhao, Haitao; Lee, Simon Ming-Yuen; Wang, Xueqing; Zheng, Ying

2017-08-01

With the wide application of nanotechnology to drug delivery systems, a simple, dynamic and visual in vivo model for high-throughput screening of novel formulations with fluorescence markers across biological barriers is desperately needed. In vitro cell culture models have been widely used, although they are far from a complimentary in vivo system. Mammalian animal models are common predictive models to study transport, but they are costly and time consuming. Zebrafish (Danio rerio), a small vertebrate model, have the potential to be developed as an "intermediate" model for quick evaluations. Based on our previously established coumarin 6 nanocrystals (C6-NCs), which have two different sizes, the present study investigates the transportation of C6-NCs across four biological barriers, including the chorion, blood brain barrier (BBB), blood retinal barrier (BRB) and gastrointestinal (GI) barrier, using zebrafish embryos and larvae as in vivo models. The biodistribution and elimination of C6 from different organs were quantified in adult zebrafish. The results showed that compared to 200nm C6-NCs, 70nm C6-NCs showed better permeability across these biological barriers. A FRET study suggested that intact C6-NCs together with the free dissolved form of C6 were absorbed into the larval zebrafish. More C6 was accumulated in different organs after incubation with small sized NCs via lipid raft-mediated endocytosis in adult zebrafish, which is consistent with the findings from in vitro cell monolayers and the zebrafish larvae model. C6-NCs could be gradually eliminated in each organ over time. This study demonstrated the successful application of zebrafish as a simple and dynamic model to simultaneously assess the transport of nanosized drug delivery systems across several biological barriers and biodistribution in different organs, especially in the brain, which could be used for central nervous system (CNS) drug and delivery system screening. Copyright © 2017 Elsevier B

Universal trend for heavy-ion total reaction cross sections at energies above the Coulomb barrier

International Nuclear Information System (INIS)

Tavares, O.A.P.; Medeiros, E.L.; Morcelle, V.

2010-06-01

Heavy-ion total reaction cross section measurements for more than one thousand one hundred reaction cases covering 61 target nuclei in the range 6 Li- 238 U, and 158 projectile nuclei from 2 H up to 84 Kr (mostly exotic ones) have been analysed in a systematic way by using an empirical, three-parameter formula which is applicable to cases for projectile kinetic energies above the Coulomb barrier. The analysis has shown that the average total nuclear binding energy per nucleon of the interacting nuclei and their radii are the chief quantities which describe the cross section patterns. A great number of cross section data (87%) has been quite satisfactorily reproduced by the proposed formula, therefore total reaction cross section predictions for new, not yet experimentally investigated reaction cases can be obtained within 25 percent (or much less) of uncertainty (author)

Quantum chemical modeling of zeolite-catalyzed methylation reactions: toward chemical accuracy for barriers.

Science.gov (United States)

Svelle, Stian; Tuma, Christian; Rozanska, Xavier; Kerber, Torsten; Sauer, Joachim

2009-01-21

The methylation of ethene, propene, and t-2-butene by methanol over the acidic microporous H-ZSM-5 catalyst has been investigated by a range of computational methods. Density functional theory (DFT) with periodic boundary conditions (PBE functional) fails to describe the experimentally determined decrease of apparent energy barriers with the alkene size due to inadequate description of dispersion forces. Adding a damped dispersion term expressed as a parametrized sum over atom pair C(6) contributions leads to uniformly underestimated barriers due to self-interaction errors. A hybrid MP2:DFT scheme is presented that combines MP2 energy calculations on a series of cluster models of increasing size with periodic DFT calculations, which allows extrapolation to the periodic MP2 limit. Additionally, errors caused by the use of finite basis sets, contributions of higher order correlation effects, zero-point vibrational energy, and thermal contributions to the enthalpy were evaluated and added to the "periodic" MP2 estimate. This multistep approach leads to enthalpy barriers at 623 K of 104, 77, and 48 kJ/mol for ethene, propene, and t-2-butene, respectively, which deviate from the experimentally measured values by 0, +13, and +8 kJ/mol. Hence, enthalpy barriers can be calculated with near chemical accuracy, which constitutes significant progress in the quantum chemical modeling of reactions in heterogeneous catalysis in general and microporous zeolites in particular.

Role of hexadecapole deformation of projectile 28Si in heavy-ion fusion reactions near the Coulomb barrier

Science.gov (United States)

Kaur, Gurpreet; Hagino, K.; Rowley, N.

2018-06-01

The vast knowledge regarding the strong influence of quadrupole deformation β2 of colliding nuclei in heavy-ion sub-barrier fusion reactions inspires a desire to quest the sensitivity of fusion dynamics to higher order deformations, such as β4 and β6 deformations. However, such studies have rarely been carried out, especially for deformation of projectile nuclei. In this article, we investigated the role of β4 of the projectile nucleus in the fusion of the 28Si+92Zr system. We demonstrated that the fusion barrier distribution is sensitive to the sign and value of the β4 parameter of the projectile, 28Si, and confirmed that the 28Si nucleus has a large positive β4. This study opens an indirect way to estimate deformation parameters of radioactive nuclei using fusion reactions, which is otherwise difficult because of experimental constraints.

Molecular codes in biological and chemical reaction networks.

Directory of Open Access Journals (Sweden)

Dennis Görlich

Full Text Available Shannon's theory of communication has been very successfully applied for the analysis of biological information. However, the theory neglects semantic and pragmatic aspects and thus cannot directly be applied to distinguish between (bio- chemical systems able to process "meaningful" information from those that do not. Here, we present a formal method to assess a system's semantic capacity by analyzing a reaction network's capability to implement molecular codes. We analyzed models of chemical systems (martian atmosphere chemistry and various combustion chemistries, biochemical systems (gene expression, gene translation, and phosphorylation signaling cascades, an artificial chemistry, and random reaction networks. Our study suggests that different chemical systems possess different semantic capacities. No semantic capacity was found in the model of the martian atmosphere chemistry, the studied combustion chemistries, and highly connected random networks, i.e. with these chemistries molecular codes cannot be implemented. High semantic capacity was found in the studied biochemical systems and in random reaction networks where the number of second order reactions is twice the number of species. We conclude that our approach can be applied to evaluate the information processing capabilities of a chemical system and may thus be a useful tool to understand the origin and evolution of meaningful information, e.g. in the context of the origin of life.

Delivery of Biologics Across the Blood-Brain Barrier with Molecular Trojan Horse Technology.

Science.gov (United States)

Pardridge, William M

2017-12-01

Biologics are potential new therapeutics for many diseases of the central nervous system. Biologics include recombinant lysosomal enzymes, neurotrophins, decoy receptors, and therapeutic antibodies. These are large molecule drugs that do not cross the blood-brain barrier (BBB). All classes of biologics have been tested, without success, in clinical trials of brain disease over the last 25 years. In none of these past clinical trials was the biologic re-engineered to enable transport across the BBB. If the biologic does not cross the BBB, the drug cannot reach the target site in brain, and success in a clinical trial is not expected. Biologics can be re-engineered for BBB transport with the use of molecular Trojan horse technology. A BBB molecular Trojan horse is a monoclonal antibody (MAb) against an endogenous BBB receptor transporter, such as the insulin receptor or transferrin receptor. The receptor-specific MAb penetrates the brain via transport on the endogenous BBB receptor. The MAb acts as a molecular Trojan horse to deliver across the BBB the biologic pharmaceutical that is genetically fused to the MAb. The lead Trojan horse is a MAb against the human insulin receptor (HIR), and HIRMAb-derived fusion proteins have entered clinical trials for the treatment of brain disease.

[Are there pseudophototropic reactions in biology? Part 4: On the reversibility of biologic/synthetic polymere systems (author's transl)].

Science.gov (United States)

Patschorke, J

1979-01-01

In further research on pseudophototropic behaviour in cellular membranes of halobacteria the reversibility of vinylmethylethermaleic anhydride-copolymeres with biological liquids is tested and the basic principles of different colour generating reactions are studied.

Universal trend for heavy-ion total reaction cross sections at energies above the Coulomb barrier

Energy Technology Data Exchange (ETDEWEB)

Tavares, O.A.P.; Medeiros, E.L., E-mail: emil@cbpf.b [Centro Brasileiro de Pesquisas Fisicas (CBPF), Rio de Janeiro, RJ (Brazil); Morcelle, V. [Universidade de Sao Paulo (IF/USP), SP (Brazil). Inst. de Fisica

2010-06-15

Heavy-ion total reaction cross section measurements for more than one thousand one hundred reaction cases covering 61 target nuclei in the range {sup 6}Li-{sup 238}U, and 158 projectile nuclei from {sup 2}H up to {sup 84}Kr (mostly exotic ones) have been analysed in a systematic way by using an empirical, three-parameter formula which is applicable to cases for projectile kinetic energies above the Coulomb barrier. The analysis has shown that the average total nuclear binding energy per nucleon of the interacting nuclei and their radii are the chief quantities which describe the cross section patterns. A great number of cross section data (87%) has been quite satisfactorily reproduced by the proposed formula, therefore total reaction cross section predictions for new, not yet experimentally investigated reaction cases can be obtained within 25 percent (or much less) of uncertainty (author)

Reaction mechanisms in collisions induced by $^{8}$B beam close to the barrier

CERN Multimedia

The aim of the proposed experiment is to investigate the reaction dynamics of proton-halo induced collisions at energies around the Coulomb barrier where coupling to continuum effects are expected to be important. We propose to measure the $^{8}$B + $^{64}$Zn elastic scattering angular distribution together with the measurement, for the first time, of p - $^{7}$Be coincidences coming from transfer and/or break-up of $^{8}$B. The latter will allow a better understanding of the relative contribution of elastic $\\textit{vs}$ non-elastic break-up in reactions induced by extremely weakly-bound nuclei. We believe that with the availability of the post accelerated $^{8}$B beam at REX-ISOLDE we will be able to collect for the first time high quality data for the study of such an important topic.

[The hyperiricosuria as an indicator of derangement of biologic functions of endoecology and adaptation, biologic reactions of excretion, inflammation and arterial tension].

Science.gov (United States)

Titov, V N; Oshchepkova, E V; Dmitriev, V A; Gushchina, O V; Shiriaeva, Iu K; Iashin, A Ia

2012-04-01

During millions years in all animals allantoine (oxidized by uricase uric acid) was catabolite of purines and ascorbic acid was an acceptor of active forms of oxygen. The proximal tubules of nephron reabsorbed the trace amounts of uric acid Then during phylogenesis the primates had a mutation of ascorbic acid gen minus. Later on occurred a second spontaneous mutation and uricase gen minus and uric acid became catabolites of purines. In absence of ascorbic acid synthesis ions of urates became a major capturers of active forms of oxygen and all uric acid as before underwent the reabsorption. Later the carriers were formed which began in epithelium of proximal tubules to secrete all uric acid into urine. At every incident of "littering" of intercellular medium with endogenic flogogens (impairment of biologic function of endoecology) under compensatory development of biologic reaction of inflammation the need in inactivation of active forms of oxygen increases. Hence later on in phylogenesis one more stage was formed--post secretory reabsorption of uric acid In the biologic reaction of inflammation epithelium of proximal tubules initiates retentional hyperiricosuria. The general antioxidant activity of human blood plasma in 60% is presented by urates' ions. The excretion of uric acid includes 4 stages: filtration, full reabsorption, secretion and post secretory reabsorption. In phylogenesis these stages formed in sequence. The mild hyperiricosuria is most frequently considered as a non-specific indicator of activation of biologic reaction of inflammation. The productive hyperiricosuria develops more infrequently under surplus of meat food and cytolysis syndrome (intensification of cell loss in vivo). Under concentration of uric acid more than 400 mkmol/l part of urates circulates in intercellular medium in the form of crystals. The microcrystals of uric acid (biologic "litter") initiate the syndrome of systemic inflammatory response as an endogenic flogogen

The asymmetric hetero-Diels-Alder reaction in the syntheses of biologically relevant compounds.

Science.gov (United States)

Eschenbrenner-Lux, Vincent; Kumar, Kamal; Waldmann, Herbert

2014-10-13

The hetero-Diels-Alder reaction is one of the most powerful transformations in the chemistry toolbox for the synthesis of aza- and oxa-heterocycles embodying multiple stereogenic centers. However, as compared to other cycloadditions, in particular the dipolar cycloadditions and the Diels-Alder reaction, the hetero-Diels-Alder reaction has been much less explored and exploited in organic synthesis. Nevertheless, this powerful transformation has opened up efficient and creative routes to biologically relevant small molecules and different natural products which contain six-membered oxygen or nitrogen ring systems. Recent developments in this field, in particular in the establishment of enantioselectively catalyzed hetero-Diels-Alder cycloadditions steered by a plethora of different catalysts and the application of the resulting small molecules in chemical biology and medicinal chemistry research, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

What we have learned so far on reactions and scattering with weakly bound nuclei at near barrier energies

International Nuclear Information System (INIS)

Gomes, P.R.S.

2011-01-01

Reactions involving weakly bound nuclei, especially halo nuclei, at near barrier energies, are an important subject not yet fully understood. Due to the low threshold energy for breakup, this process is particularly important and may affect significantly the fusion process and elastic scattering. In this talk I will show the systematic of results so far available in this field, concerning static and dynamical effects of halo and breakup on fusion and total reaction cross sections, the energy dependence of the optical potential on the elastic scattering and coupling effects on quasi-elastic scattering barrier distributions involving weakly bound nuclei, both stable and radioactive. The data to be discussed are new data from our group and from the literature, together with some older data. I will also present some experimental challenges for the development of this field. (author)

Study of the (3He,d) reactions on 58Ni, 60Ni and 56Fe near the Coulomb barrier

International Nuclear Information System (INIS)

Baghdadi, A.; Seltz, R.; Magnac-Valette, D.; Bonneaud, G.; Gerardin, C.

1975-01-01

Using spectroscopic information gained by earlier measurements of the proton bound states populated by stripping reactions, ( 3 He,d) reactions on 58 Ni, 60 Ni and 56 Fe targets are studied at energies near the Coulomb barrier and evaluation is made of the vertex function 3 He>. This value is then used to determine spectroscopic factors for low-lying states in 57 Co [fr

Hydraulic performance of permeable barriers for in situ treatment of contaminated groundwater

International Nuclear Information System (INIS)

Smyth, D.J.A.; Shikaze, S.G.; Cherry, J.A.

1997-01-01

The passive interception and in situ treatment of dissolved contaminants in groundwater by permeable reactive barriers has recently gained favor at an increasing number of sites as an alternative to conventional approaches to groundwater remediation such as the pump-and-treat method. Permeable reactive barriers have two essential functions. The first is that the barriers must be installed in a position such that all of the plume passes through the reactive system. The second function is to achieve acceptable treatment of the contamination by physical, chemical or biological means within or downgradient of the barrier. In this paper, issues associated with the hydraulic performance of permeable reaction barriers are evaluated using a three-dimensional groundwater flow model. The efficiency of plume capture by permeable wall and funnel-and-gate systems is examined for some generic and for site-specific hydrogeologic systems. The results have important implications to decisions pertaining to the selection, design and installation of permeable reactive barrier systems

Organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds

International Nuclear Information System (INIS)

Maltsev, O V; Beletskaya, Irina P; Zlotin, Sergei G

2011-01-01

Recent applications of organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds: natural products, pharmaceutical agents and plant protection agents are reviewed. The key mechanisms of stereoinduction, types of organocatalysts and reagents used in these reactions are considered. The material is classified according to the type of newly formed bonds incorporating the asymmetric carbon atom, and the information for the most numerous C–C coupling reactions is systematized according to the natures of the electrophile and the nucleophile. The bibliography includes 433 references.

Breaching Biological Barriers: Protein Translocation Domains as Tools for Molecular Imaging and Therapy

Directory of Open Access Journals (Sweden)

Benjamin L. Franc

2003-10-01

Full Text Available The lipid bilayer of a cell presents a significant barrier for the delivery of many molecular imaging reagents into cells at target sites in the body. Protein translocation domains (PTDs are peptides that breach this barrier. Conjugation of PTDs to imaging agents can be utilized to facilitate the delivery of these agents through the cell wall, and in some cases, into the cell nucleus, and have potential for in vitro and in vivo applications. PTD imaging conjugates have included small molecules, peptides, proteins, DNA, metal chelates, and magnetic nanoparticles. The full potential of the use of PTDs in novel in vivo molecular probes is currently under investigation. Cells have been labeled in culture using magnetic nanoparticles derivatized with a PTD and monitored in vivo to assess trafficking patterns relative to cells expressing a target antigen. In vivo imaging of PTD-mediated gene transfer to cells of the skin has been demonstrated in living animals. Here we review several natural and synthetic PTDs that have evolved in the quest for easier translocation across biological barriers and the application of these peptide domains to in vivo delivery of imaging agents.

Fusion barriers in heavy ion collisions

International Nuclear Information System (INIS)

Zhu Long; Su Jun; Xie Wenjie; Guo Chenchen; Zhang Donghong; Zhang Fengshou

2014-01-01

Study of fusion barrier is very important for people to better understand fusion reactions. In this paper the Improved Isospin-dependent Quantum Molecular Dynamics (ImIQMD) model is introduced firstly. Then the shell correction effects, energy dependence, isospin effects and orientation effects of fusion barrier are studied. The fusion barriers for the fusion reactions "4"0Ca + "4"0Ca, "4"8Ca + "2"0"8Pb, "4"8Ca + "2"0"4Pb and "1"6O + "1"5"4Sm are extracted. The negative shell correction energies lower potential barriers of a certain reaction. A complex phenomenon of energy dependence is observed. It is also found that incident energy dependence of the barrier radius and barrier height shows opposite behaviors. The Coulomb potential shows weak energy dependence when distance of two colliding nuclei is lower than the touching distance. The isospin effects of the potential barrier are investigated. The orientation effects of the potential barrier are also discussed for the system "1"6O + "1"5"4Sm. (authors)

Sensitivity of fusion and quasi-elastic barrier distributions of {sub 16}O+{sub 144}Sm reaction on the coupling radius parameter

Energy Technology Data Exchange (ETDEWEB)

Zamrun, Muhammad; Usman, Ida; Variani, Viska Inda [Department of Physics, Haluoleo University, Kendari, Sulawesi Tengagra, 93232 (Indonesia); Kassim, Hasan Abu [Department of Physics, University of Malaya, 50603 Kuala Lumpur (Malaysia)

2014-03-05

We study the heavy-ion collision at sub-barrier energies of {sub 16}O+{sub 144}Sm system using full order coupled-channels formalism. We especially investigate the sensitivity of fusion and quasi-elastic barrier distributions for this system on the coupling radius parameter. We found that the coupled-channels calculations of the fusion and the quasi-elastic barrier distributions are sensitive to the coupling radius for this reaction in contrast to the fusion and quasi-elastic cross section. Our study indicates that the larger coupling radius, i.e., r{sub coup}=1.20, is required by the experimental quasi-elastic barrier distribution. However, the experimental fusion barrier distribution compulsory the small value, i.e., r{sub coup}=1.06.

Reaction dynamics studies for the system 7Be + 208Pb at Coulomb barrier energies

Directory of Open Access Journals (Sweden)

Mazzocco M.

2017-01-01

Full Text Available The scattering process of the Radioactive Ion Beam 7Be from a 208Pb target was measured at three near-barrier energies. The quasi-elastic angular distributions were analyzed within the framework of the optical model to extract the reaction cross sections. The results are compared with those obtained for the reactions induced by the mirror projectile 7Li and by the lightest particle-stable lithium isotope 6Li on the same target. The angular distributions for the production of the two 7Be constituent clusters, namely 3He and 4He, were also measured. In agreement with what observed for the interaction of 7Be with lighter targets, the production of the heavier helium isotope resulted to be much more abundant than that of its lighter counterpart.

Reaction dynamics studies for the system 7Be + 208Pb at Coulomb barrier energies

Science.gov (United States)

Mazzocco, M.; Boiano, A.; Boiano, C.; La Commara, M.; Manea, C.; Parascandolo, C.; Pierroutsakou, D.; Strano, E.; Torresi, D.; Acosta, L.; Di Meo, P.; Fernandez-Garcia, J. P.; Glodariu, T.; Grebosz, J.; Guglielmetti, A.; Marquinez-Duran, G.; Martel, I.; Nicoletto, M.; Pakou, A.; Sánchez-Benítez, A. M.; Sava, T.; Sgouros, O.; Signorini, C.; Soramel, F.; Soukeras, V.; Stroe, L.

2017-11-01

The scattering process of the Radioactive Ion Beam 7Be from a 208Pb target was measured at three near-barrier energies. The quasi-elastic angular distributions were analyzed within the framework of the optical model to extract the reaction cross sections. The results are compared with those obtained for the reactions induced by the mirror projectile 7Li and by the lightest particle-stable lithium isotope 6Li on the same target. The angular distributions for the production of the two 7Be constituent clusters, namely 3He and 4He, were also measured. In agreement with what observed for the interaction of 7Be with lighter targets, the production of the heavier helium isotope resulted to be much more abundant than that of its lighter counterpart.

Cross-sections and average angular momenta in fusion reactions near the coulomb barrier

International Nuclear Information System (INIS)

Dasgupta, M.

1992-01-01

In recent years there has been an increasing interest in the study of heavy ion collisions near the Coulomb barrier. This has been triggered mainly by the observations of enhancements by factors of about one to two order of magnitude in sub-Coulomb barrier fusion (SBF) cross-sections between medium mass nuclei, as compared to predictions based on one-dimensional barrier penetration model (l-d BPM). Though, a considerable amount of work both theoretical and experimental has been done in this field, a complete understanding of the SBF phenomenon has not yet been achieved. The relation between fusion excitation function and angular momentum (l) distribution in SBF reactions is a topic of current interest. It is believed that l-distributions provide a more stringent test of SBF models that the excitation functions alone. Simultaneous measurement of l-distribution (or its moments) and fusion excitation function is expected to lead to a better understanding of the relationship between these two qualities. Such information has been obtained in experiments done at pelletron accelerator facility. In the present talk the measurement of fusion cross-sections and the method of determination of average l from partial evaporation residue cross-section has been elaborated. An analysis of the experimental data on the basis of some of the SBF models has been discussed briefly. (author). 13 refs

Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

Science.gov (United States)

Khavrutskii, Ilja V; Smith, Jason B; Wallqvist, Anders

2013-10-28

Here, we apply the harmonic Fourier beads (HFB) path optimization method to study chemical reactions involving covalent bond breaking and forming on quantum mechanical (QM) and hybrid QM∕molecular mechanical (QM∕MM) potential energy surfaces. To improve efficiency of the path optimization on such computationally demanding potentials, we combined HFB with conjugate gradient (CG) optimization. The combined CG-HFB method was used to study two biologically relevant reactions, namely, L- to D-alanine amino acid inversion and alcohol acylation by amides. The optimized paths revealed several unexpected reaction steps in the gas phase. For example, on the B3LYP∕6-31G(d,p) potential, we found that alanine inversion proceeded via previously unknown intermediates, 2-iminopropane-1,1-diol and 3-amino-3-methyloxiran-2-ol. The CG-HFB method accurately located transition states, aiding in the interpretation of complex reaction mechanisms. Thus, on the B3LYP∕6-31G(d,p) potential, the gas phase activation barriers for the inversion and acylation reactions were 50.5 and 39.9 kcal∕mol, respectively. These barriers determine the spontaneous loss of amino acid chirality and cleavage of peptide bonds in proteins. We conclude that the combined CG-HFB method further advances QM and QM∕MM studies of reaction mechanisms.

Dielectric barrier discharges applied for soft ionization and their mechanism

Energy Technology Data Exchange (ETDEWEB)

Brandt, Sebastian; Klute, Felix David; Schütz, Alexander; Franzke, Joachim, E-mail: joachim.franzke@isas.de

2017-01-25

Dielectric barrier discharges are used for analytical applications as dissociative source for optical emission spectrometry and for ambient-ionization techniques. In the range of ambient-ionization techniques it has attracted much attention in fields like food safety, biological analysis, mass spectrometry for reaction monitoring and imaging forensic identification. In this review some examples are given for the application as desorption/ionization source as well as for the sole application as ionization source with different sample introductions. It will be shown that the detection might depend on the certain distance of the plasma in reference to the sample or the kind of discharge which might be produced by different shapes of the applied high voltage. Some attempts of characterization are presented. A more detailed characterization of the dielectric barrier discharge realized with two ring electrodes, each separately covered with a dielectric layer, is described. - Highlights: • Dielectric barrier discharge applied as desorption/ionization source. • Dielectric barrier discharge applied solely as ionization source. • Different geometries in order to maintain soft ionization. • Characterization of the LTP probe. • Dielectric barrier discharges with two dielectric barriers (ring-ring shape).

Collisions between heavy nuclei near the barrier

International Nuclear Information System (INIS)

Henning, W.

1988-05-01

Detailed information has recently become available on the reaction behavior in very heavy nuclear systems close to the Coulomb barrier. Starting from an experimental study of the distribution of the reaction strength above and below the barrier, the dominant reaction channels of quasi-elastic and strongly-damped processes are examined. With decreasing incident energy, the sub-barrier collisions are increasingly dominated by quasi-elastic processes. From the division of internal excitation energy, new information is obtained on the nature of the dissipative processes. (orig.)

Connective tissue graft as a biological barrier for guided tissue regeneration in intrabony defects: a histological study in dogs.

Science.gov (United States)

Ribeiro, Fernando Salimon; Pontes, Ana Emília Farias; Zuza, Elizangela Partata; da Silva, Vanessa Camila; Lia, Raphael Carlos Comelli; Marcantonio Junior, Elcio

2015-06-01

The use of the autogenous periosteal graft as biological barrier has been proposed for periodontal regeneration. The aim of this study was to evaluate the histometric findings of the subepithelial connective tissue graft as barrier in intrabony defects compared to a bioabsorbable membrane. Three-walled intrabony defects were created surgically in the mesial aspect of the right and left maxillary canines in five healthy mongrel dogs. The defects were chronified, and two types of barriers were randomly carried out for guided tissue regeneration in a split-mouth design: the test group with a subepithelial connective tissue graft and the control group with a bioabsorbable membrane. The specimens were processed for histometric analyses of the epithelium (E), connective tissue (CT), newly formed cementum (NC), new bone (NB), and total newly formed tissues (NFT). The test side showed smaller mean of NC (3.6 ± 1.2), NB (2.1 ± 0.7), and NFT (7.7 ± 0.8) than the control group (NC 7.3 ± 0.5; NB 5.3 ± 1.3; NFT 10.1 ± 2.2; P  0.05) and CT (test 2.5 ± 1.1; control 2.0 ± 0.5; P > 0.05) between groups. The bioabsorbable membrane was more effective in maintaining the space for periodontal regeneration than periosteal connective graft when used as barrier. The bioabsorbable membrane showed more favorable regenerative results in intrabony defects in dogs than the subepithelial connective tissue graft as biological barrier.

Microbial diversity and structure are drivers of the biological barrier effect against Listeria monocytogenes in soil.

Science.gov (United States)

Vivant, Anne-Laure; Garmyn, Dominique; Maron, Pierre-Alain; Nowak, Virginie; Piveteau, Pascal

2013-01-01

Understanding the ecology of pathogenic organisms is important in order to monitor their transmission in the environment and the related health hazards. We investigated the relationship between soil microbial diversity and the barrier effect against Listeria monocytogenes invasion. By using a dilution-to-extinction approach, we analysed the consequence of eroding microbial diversity on L. monocytogenes population dynamics under standardised conditions of abiotic parameters and microbial abundance in soil microcosms. We demonstrated that highly diverse soil microbial communities act as a biological barrier against L. monocytogenes invasion and that phylogenetic composition of the community also has to be considered. This suggests that erosion of diversity may have damaging effects regarding circulation of pathogenic microorganisms in the environment.

Densification of Ce0.9Gd0.1O1.95 barrier layer by in-situ solid state reaction

DEFF Research Database (Denmark)

Ni, De Wei; Esposito, Vincenzo

2014-01-01

A novel methodology, called in-situ solid state reaction (SSR), is developed and achieved for the densification of gadolinia doped ceria (CGO) barrier layer (BL) within the solid oxide fuel cell (SOFC) technology. The method is based on the combined use of impregnation technique and a designed two...

Applications of the absolute reaction rate theory to biological responses in electric and magnetic fields

International Nuclear Information System (INIS)

Brannen, J.P.; Wayland, J.R.

1976-01-01

This paper develops a theoretical foundation for the study of biological responses of electric and magnetic fields. The basis of the development is the absolute reaction rate theory and the effects of fields on reaction rates. A simple application to the response of Bacillus subtilis var niger in a microwave field is made. Potential areas of application are discussed

Fusion cross sections for 6,7Li + 24Mg reactions at energies below and above the barrier

International Nuclear Information System (INIS)

Ray, M.; Mukherjee, A.; Pradhan, M. K.; Kshetri, Ritesh; Sarkar, M. Saha; Dasmahapatra, B.; Palit, R.; Majumdar, I.; Joshi, P. K.; Jain, H. C.

2008-01-01

Measurement of fusion cross sections for the 6,7 Li + 24 Mg reactions by the characteristic γ-ray method has been done at energies from below to well above the respective Coulomb barriers. The fusion cross sections obtained from these γ-ray cross sections for the two systems are found to agree well with the total reaction cross sections at low energies. The relatively large difference between total cross sections and measured fusion cross sections at higher energies is consistent with the fact that other channels, in particular breakup, open up with an increase of bombarding energy. The breakup channel, however, appears not to have any influence on fusion cross sections. The critical angular momenta (l cr ) deduced from the fusion cross sections are found to have an energy dependence similar to other Li-induced reactions

Barriers to fusion

International Nuclear Information System (INIS)

Berriman, A.C.; Butt, R.D.; Dasgupta, M.; Hinde, D.J.; Morton, C.R.; Newton, J.O.

1999-01-01

The fusion barrier is formed by the combination of the repulsive Coulomb and attractive nuclear forces. Recent research at the Australian National University has shown that when heavy nuclei collide, instead of a single fusion barrier, there is a set of fusion barriers. These arise due to intrinsic properties of the interacting nuclei such deformation, rotations and vibrations. Thus the range of barrier energies depends on the properties of both nuclei. The transfer of matter between nuclei, forming a neck, can also affect the fusion process. High precision data have been used to determine fusion barrier distributions for many nuclear reactions, leading to new insights into the fusion process

Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

Science.gov (United States)

Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

2017-07-06

The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

Reaction mechanisms in heavy ion fusion

Directory of Open Access Journals (Sweden)

Lubian J.

2011-10-01

Full Text Available We discuss the reaction mechanisms involved in heavy ion fusion. We begin with collisions of tightly bound systems, considering three energy regimes: energies above the Coulomb barrier, energies just below the barrier and deep sub-barrier energies. We show that channel coupling effects may influence the fusion process at above-barrier energies, increasing or reducing the cross section predicted by single barrier penetration model. Below the Coulomb barrier, it enhances the cross section, and this effect increases with the system’s size. It is argued that this behavior can be traced back to the increasing importance of Coulomb coupling with the charge of the collision partners. The sharp drop of the fusion cross section observed at deep sub-barrier energies is addressed and the theoretical approaches to this phenomenon are discussed. We then consider the reaction mechanisms involved in fusion reactions of weakly bound systems, paying particular attention to the calculations of complete and incomplete fusion available in the literature.

Potential surfaces in symmetric heavy-ion reactions

International Nuclear Information System (INIS)

Royer, G.; Piller, C.; Mignen, J.; Raffray, Y.

1989-01-01

The entrance channel in symmetric heavy-ion reactions is studied in the liquid-drop model approach including the nuclear proximity energy and allowing ellipsoidal deformations of the colliding nuclei. In the whole mass range a sudden transition occurs from oblate to prolate shapes when the proximity forces become important. This strongly affects the effective moment of inertia. The ellipsoidal deformations reduce the fusion barrier width for light systems and lower the potential barrier height for medium and heavy nuclei. The results are in agreement with the empirical effective barrier shift determined by Aguiar et al for the 58 Ni + 58 Ni, 74 Ge + 74 Ge and 80 Se + 80 Se systems. The sub-barrier fusion enhancement in heavy-ion reactions might be explained by the slowness of the process. Below the static fusion barrier, the reaction time is long; allowing some adiabaticity and deformations of the colliding ions. Above the barrier, the reaction is more sudden and the deformation degree of freedom is frozen

Chemisorption on size-selected metal clusters: activation barriers and chemical reactions for deuterium and aluminum cluster ions

International Nuclear Information System (INIS)

Jarrold, M.F.; Bower, J.E.

1988-01-01

The authors describe a new approach to investigating chemisorption on size-selected metal clusters. This approach involves investigating the collision-energy dependence of chemisorption using low-energy ion beam techniques. The method provides a direct measure of the activation barrier for chemisorption and in some cases an estimate of the desorption energy as well. They describe the application of this technique to chemisorption of deuterium on size-selected aluminum clusters. The activation barriers increase with cluster size (from a little over 1 eV for Al 10 + to around 2 eV for Al 27 + ) and show significant odd-even oscillations. The activation barriers for the clusters with an odd number of atoms are larger than those for the even-numbered clusters. In addition to chemisorption of deuterium onto the clusters, chemical reactions were observed, often resulting in cluster fragmentation. The main products observed were Al/sub n-1/D + , Al/sub n-2/ + , and Al + for clusters with n + and Al/sub n-1/D + for the larger clusters

Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

Directory of Open Access Journals (Sweden)

Burkhard Koenig

2011-01-01

Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

Total reaction cross section for 12C+16O below the Coulomb barrier

International Nuclear Information System (INIS)

Cujec, B.; Barnes, C.A.

1976-01-01

The energy dependence of the total reaction cross section, sigma(E), for 12 C+ 16 0 has been measured over the range Esub(c.m.)=4-12 MeV, by detecting γ-rays from the various possible residual nuclei with two large NaI(Tl) detectors placed close to the target. This technique for measuring total reaction cross sections was explored in some detail and shown to yield reliable values for sigma(E). Although the principal emphasis of this work was placed on obtaining reliable cross sections, a preliminary study has been made of the suitability of various methods for extrapolating the cross section to still lower energies. The statistical model provides a good fit with a reasonable value for the strength function, 2 >/ =6.8x10 -2 , over the range Esub(c.m.)=6.5-12 MeV, but predicts cross sections which are much too large for Esub(c.m.)<6.5 MeV. Optical model fits at low energies are especially sensitive to the radius and diffuseness of the imaginary component of the potential and, since these are still poorly known at present, such extrapolations may be wrong by orders of magnitude. A simple barrier penetration model gives a moderately good fit to the data and seems to provide the safest extrapolation to lower energies at the present time. It is clear, however, that our knowledge of the heavy-ion reaction mechanism at low energies is incomplete, and that cross-section measurements at still lower energies are needed to establish the correct procedure for extrapolating heavy-ion reaction cross sections to low energies. (Auth.)

Permeating disciplines: Overcoming barriers between molecular simulations and classical structure-function approaches in biological ion transport.

Science.gov (United States)

Howard, Rebecca J; Carnevale, Vincenzo; Delemotte, Lucie; Hellmich, Ute A; Rothberg, Brad S

2018-04-01

Ion translocation across biological barriers is a fundamental requirement for life. In many cases, controlling this process-for example with neuroactive drugs-demands an understanding of rapid and reversible structural changes in membrane-embedded proteins, including ion channels and transporters. Classical approaches to electrophysiology and structural biology have provided valuable insights into several such proteins over macroscopic, often discontinuous scales of space and time. Integrating these observations into meaningful mechanistic models now relies increasingly on computational methods, particularly molecular dynamics simulations, while surfacing important challenges in data management and conceptual alignment. Here, we seek to provide contemporary context, concrete examples, and a look to the future for bridging disciplinary gaps in biological ion transport. This article is part of a Special Issue entitled: Beyond the Structure-Function Horizon of Membrane Proteins edited by Ute Hellmich, Rupak Doshi and Benjamin McIlwain. Copyright © 2017 Elsevier B.V. All rights reserved.

Oxygen plasma etching of graphene: A first-principles dynamical inspection of the reaction mechanisms and related activation barriers

Science.gov (United States)

Koizumi, Kenichi; Boero, Mauro; Shigeta, Yasuteru; Oshiyama, Atsushi; Dept. of Applied Physics Team; Institute of Physics and Chemistry of Strasbourg (IPCMS) Collaboration; Department Of Materials Engineering Science Collaboration

2013-03-01

Oxygen plasma etching is a crucial step in the fabrication of electronic circuits and has recently received a renovated interest in view of the realization of carbon-based nanodevices. In an attempt at unraveling the atomic-scale details and to provide guidelines for the control of the etching processes mechanisms, we inspected the possible reaction pathways via reactive first principles simulations. These processes involve breaking and formation of several chemical bonds and are characterized by different free-energy barriers. Free-energy sampling techniques (metadynamics and blue moon), used to enhance the standard Car-Parrinello molecular dynamics, provide us a detailed microscopic picture of the etching of graphene surfaces and a comprehensive scenario of the activation barriers involved in the various steps. MEXT, Japan - contract N. 22104005

Benchmarking density functional tight binding models for barrier heights and reaction energetics of organic molecules.

Science.gov (United States)

Gruden, Maja; Andjeklović, Ljubica; Jissy, Akkarapattiakal Kuriappan; Stepanović, Stepan; Zlatar, Matija; Cui, Qiang; Elstner, Marcus

2017-09-30

Density Functional Tight Binding (DFTB) models are two to three orders of magnitude faster than ab initio and Density Functional Theory (DFT) methods and therefore are particularly attractive in applications to large molecules and condensed phase systems. To establish the applicability of DFTB models to general chemical reactions, we conduct benchmark calculations for barrier heights and reaction energetics of organic molecules using existing databases and several new ones compiled in this study. Structures for the transition states and stable species have been fully optimized at the DFTB level, making it possible to characterize the reliability of DFTB models in a more thorough fashion compared to conducting single point energy calculations as done in previous benchmark studies. The encouraging results for the diverse sets of reactions studied here suggest that DFTB models, especially the most recent third-order version (DFTB3/3OB augmented with dispersion correction), in most cases provide satisfactory description of organic chemical reactions with accuracy almost comparable to popular DFT methods with large basis sets, although larger errors are also seen for certain cases. Therefore, DFTB models can be effective for mechanistic analysis (e.g., transition state search) of large (bio)molecules, especially when coupled with single point energy calculations at higher levels of theory. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Effects of reaction channels in subbarrier fusion reactions

International Nuclear Information System (INIS)

Dasso, C.H.

1984-01-01

In this lecture we consider some aspects of fusion reactions between heavy ions at bombarding energies which are below or close to that of the Coulomb barrier. This problem has been traditionally confronted with simple barrier penetration calculations. So we start with a very brief review of what we can call the ''conventional'' procedure. (orig.)

Manipulating and Monitoring On-Surface Biological Reactions by Light-Triggered Local pH Alterations.

Science.gov (United States)

Peretz-Soroka, Hagit; Pevzner, Alexander; Davidi, Guy; Naddaka, Vladimir; Kwiat, Moria; Huppert, Dan; Patolsky, Fernando

2015-07-08

Significant research efforts have been dedicated to the integration of biological species with electronic elements to yield smart bioelectronic devices. The integration of DNA, proteins, and whole living cells and tissues with electronic devices has been developed into numerous intriguing applications. In particular, the quantitative detection of biological species and monitoring of biological processes are both critical to numerous areas of medical and life sciences. Nevertheless, most current approaches merely focus on the "monitoring" of chemical processes taking place on the sensing surfaces, and little efforts have been invested in the conception of sensitive devices that can simultaneously "control" and "monitor" chemical and biological reactions by the application of on-surface reversible stimuli. Here, we demonstrate the light-controlled fine modulation of surface pH by the use of photoactive molecularly modified nanomaterials. Through the use of nanowire-based FET devices, we showed the capability of modulating the on-surface pH, by intensity-controlled light stimulus. This allowed us simultaneously and locally to control and monitor pH-sensitive biological reactions on the nanodevices surfaces, such as the local activation and inhibition of proteolytic enzymatic processes, as well as dissociation of antigen-antibody binding interactions. The demonstrated capability of locally modulating the on-surface effective pH, by a light stimuli, may be further applied in the local control of on-surface DNA hybridization/dehybridization processes, activation or inhibition of living cells processes, local switching of cellular function, local photoactivation of neuronal networks with single cell resolution and so forth.

Theoretical study on the mechanism of the reaction of FOX-7 with OH and NO2 radicals: bimolecular reactions with low barrier during the decomposition of FOX-7

Science.gov (United States)

Zhang, Ji-Dong; Zhang, Li-Li

2017-12-01

The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.

Traveling wave solutions of a biological reaction-convection-diffusion equation model by using $(G'/G$ expansion method

Directory of Open Access Journals (Sweden)

Shahnam Javadi

2013-07-01

Full Text Available In this paper, the $(G'/G$-expansion method is applied to solve a biological reaction-convection-diffusion model arising in mathematical biology. Exact traveling wave solutions are obtained by this method. This scheme can be applied to a wide class of nonlinear partial differential equations.

Coupled modelling (transport-reaction) of the fluid-clay interactions and their feed back on the physical properties of the bentonite engineered clay barrier system; Modelisation couplee (transport - reaction) des interactions fluides - argiles et de leurs effets en retour sur les proprietes physiques de barrieres ouvragees en bentonite

Energy Technology Data Exchange (ETDEWEB)

Marty, N

2006-11-15

The originality of this work is to process feed back effects of mineralogical and chemical modifications of clays, in storage conditions, on their physical properties and therefore on their transport characteristics (porosity, molecular diffusion, permeability). These feed back effects are modelled using the KIRMAT code (Kinetic of Reaction and MAss Transfer) developed from the kinetic code KINDIS by adding the effect of water renewal in the mineral-solution reactive cells. KIRMAT resolves mass balance equations associated with mass transport together with the geochemical reactions in a 1D approach. After 100 000 years of simulated interaction at 100 C, with the fluid of the Callovo-Oxfordian geological level (COX) and with iron provided by the steel overpack corrosion, the montmorillonite of the clay barrier is only partially transformed (into illite, chlorite, saponite...). Only outer parts of the modelled profile seem to be significantly affected by smectite dissolution processes, mainly at the interface with the geological environment. The modifications of physical properties show a closure of the porosity at the boundaries of the barrier, by creating a decrease of mass transport by molecular diffusion, essentially at the interface with the iron. Permeability laws applied to this system show a decrease of the hydraulic conductivity correlated with the porosity evolution. Near the COX, the swelling pressure of the clays from the barrier decreases. In the major part of the modelled profile, the engineered clay barrier system seems to keep its initial physical properties (porosity, molecular diffusion, permeability, swelling pressure) and functionalities. (author)

Sub-barrier capture with quantum diffusion approach

Directory of Open Access Journals (Sweden)

Scheid W.

2011-10-01

Full Text Available With the quantum diffusion approach the behavior of capture cross sections and mean-square angular momenta of captured systems are revealed in the reactions with deformed and spherical nuclei at sub-barrier energies. With decreasing bombarding energy under the barrier the external turning point of the nucleus-nucleus potential leaves the region of short-range nuclear interaction and action of friction. Because of this change of the regime of interaction, an unexpected enhancement of the capture cross section is found at bombarding energies far below the Coulomb barrier. This effect is shown its worth in the dependence of mean-square angular momentum on the bombarding energy. From the comparison of calculated capture cross sections and experimental capture or fusion cross sections the importance of quasifission near the entrance channel is demonstrated for the actinidebased reactions and reactions with medium-heavy nuclei at extreme sub-barrier energies.

Analysis of complete fusion excitation functions for 7Li+152Sm, 197Au and 209Bi reactions at around barrier energies

International Nuclear Information System (INIS)

Kharab, Rajesh; Chahal, Rajiv; Kumar, Rajiv

2017-01-01

In the present work we have analyzed the fusion excitation function for CF process using the simple Wong’s formula in conjunction with the energy dependent Woods-Saxon potential (EDWSP) in near barrier energy region for 7 Li+ 152 Sm, 197 Au and 209 Bi reactions

Calcium-Magnesium-Alumino-Silicates (CMAS) Reaction Mechanisms and Resistance of Advanced Turbine Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites

Science.gov (United States)

Zhu, Dongming; Costa, Gustavo; Harder, Bryan J.; Wiesner, Valerie L.; Hurst, Janet B.; Puleo, Bernadette J.

2017-01-01

Environmental barrier coatings (EBCs) and SiC/SiC ceramic matrix composites (CMCs) systems will play a crucial role in future turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is an essential requirement to enable the applications of the 2700-3000 F EBC - CMC systems. This presentation primarily focuses on the reaction mechanisms of advanced NASA environmental barrier coating systems, when in contact with Calcium-Magnesium Alumino-Silicates (CMAS) at high temperatures. Advanced oxide-silicate defect cluster environmental barrier coatings are being designed for ultimate balanced controls of the EBC temperature capability and CMAS reactivity, thus improving the CMAS resistance. Further CMAS mitigation strategies are also discussed.

Towards a converged barrier height for the entrance channel transition state of the N( 2D) + CH 4 reaction and its implication for the chemistry in Titan's atmosphere

Science.gov (United States)

Ouk, Chanda-Malis; Zvereva-Loëte, Natalia; Bussery-Honvault, Béatrice

2011-10-01

The N( 2D) + CH 4 reaction appears to be a key reaction for the chemistry of Titan's atmosphere, opening the door to nitrile formation as recently observed by the Cassini-Huygens mission. Faced to the controversy concerning the existence or not of a potential barrier for this reaction, we have carried out accurate ab initio calculations by means of multi-state multi-reference configuration interaction (MS-MR-SDCI) method. These calculations have been partially corrected for the size-consistency errors (SCE) by Davidson, Pople or AQCC corrections. We suggest a barrier height of 3.86 ± 0.84 kJ/mol, including ZPE, for the entrance transition state, in good agreement with the experimental value. Its implication in Titan's atmopsheric chemistry is discussed.

Frontiers in Cancer Nanomedicine: Directing Mass Transport through Biological Barriers

Science.gov (United States)

Ferrari, Mauro

2010-01-01

The physics of mass transport within body compartments and across biological barriers differentiates cancers from healthy tissues. Variants of nanoparticles can be manufactured in combinatorially large sets, varying only one transport-affecting design parameter at a time. Nanoparticles can also be used as building blocks for systems that perform sequences of coordinated actions, in accordance to a prescribed logic. These are referred to as Logic-Embedded Vectors “(LEV)” in the following. Nanoparticles and LEVs are ideal probes for the determination of mass transport laws in tumors, acting as imaging contrast enhancers, and can be employed for the lesion-selective delivery of therapy. Their size, shape, density and surface chemistry dominate convective transport in the blood stream, margination, cell adhesion, selective cellular uptake, as well as sub-cellular trafficking and localization. As argued here, the understanding of transport differentials in cancer, termed ‘transport oncophysics’ unveils a new promising frontier in oncology: the development of lesion-specific delivery particulates that exploit mass transport differentials to deploy treatment of greater efficacy and reduced side effects. PMID:20079548

Interpretation of quasi-elastic barrier distributions for weakly bound systems

International Nuclear Information System (INIS)

Monteiro, D.S.; Gomes, P.R.S.; Lubian, J.

2009-01-01

Full text: We verify that quasi-elastic (elastic + inelastic) backscattering barrier distributions for weakly bound systems do not strictly correspond to fusion barrier distributions, but rather to reaction threshold distribution, as proposed by Zagrebaev in a recent paper concerning very heavy systems. In this work, we investigate whether Zagrebaevs interpretation is valid by comparing experimental results obtained in two very recent works with the 6 Li + 144 Sm system. Monteiro et al derived the quasi-elastic barrier distribution (or reaction threshold distribution, following Zagrebaevs interpretation) by adding elastic and inelastic backscattering for this system. Rath et al obtained fusion barrier distribution for the same system from the measured complete fusion cross section for the same system. We conclude that the quasi-elastic barrier distributions can be associated with fusion barrier distributions only in situations where there are no relevant reaction channels apart from fusion. This is not the situation for very heavy nor for weakly bound systems. (author)

Skin barrier function

DEFF Research Database (Denmark)

2016-01-01

Renowned experts present the latest knowledge Although a very fragile structure, the skin barrier is probably one of the most important organs of the body. Inward/out it is responsible for body integrity and outward/in for keeping microbes, chemicals, and allergens from penetrating the skin. Since...... the role of barrier integrity in atopic dermatitis and the relationship to filaggrin mutations was discovered a decade ago, research focus has been on the skin barrier, and numerous new publications have become available. This book is an interdisciplinary update offering a wide range of information...... on the subject. It covers new basic research on skin markers, including results on filaggrin and on methods for the assessment of the barrier function. Biological variation and aspects of skin barrier function restoration are discussed as well. Further sections are dedicated to clinical implications of skin...

Electron spin interactions in chemistry and biology fundamentals, methods, reactions mechanisms, magnetic phenomena, structure investigation

CERN Document Server

Likhtenshtein, Gertz

2016-01-01

This book presents the versatile and pivotal role of electron spin interactions in nature. It provides the background, methodologies and tools for basic areas related to spin interactions, such as spin chemistry and biology, electron transfer, light energy conversion, photochemistry, radical reactions, magneto-chemistry and magneto-biology. The book also includes an overview of designing advanced magnetic materials, optical and spintronic devices and photo catalysts. This monograph appeals to scientists and graduate students working in the areas related to spin interactions physics, biophysics, chemistry and chemical engineering.

The biological significance of brain barrier mechanisms

DEFF Research Database (Denmark)

Saunders, Norman R; Habgood, Mark D; Møllgård, Kjeld

2016-01-01

, but more work is required to evaluate the method before it can be tried in patients. Overall, our view is that much more fundamental knowledge of barrier mechanisms and development of new experimental methods will be required before drug targeting to the brain is likely to be a successful endeavor......Barrier mechanisms in the brain are important for its normal functioning and development. Stability of the brain's internal environment, particularly with respect to its ionic composition, is a prerequisite for the fundamental basis of its function, namely transmission of nerve impulses....... In addition, the appropriate and controlled supply of a wide range of nutrients such as glucose, amino acids, monocarboxylates, and vitamins is also essential for normal development and function. These are all cellular functions across the interfaces that separate the brain from the rest of the internal...

Reaction energetics on long-range corrected density functional theory: Diels-Alder reactions.

Science.gov (United States)

Singh, Raman K; Tsuneda, Takao

2013-02-15

The possibility of quantitative reaction analysis on the orbital energies of long-range corrected density functional theory (LC-DFT) is presented. First, we calculated the Diels-Alder reaction enthalpies that have been poorly given by conventional functionals including B3LYP functional. As a result, it is found that the long-range correction drastically improves the reaction enthalpies. The barrier height energies were also computed for these reactions. Consequently, we found that dispersion correlation correction is also crucial to give accurate barrier height energies. It is, therefore, concluded that both long-range exchange interactions and dispersion correlations are essentially required in conventional functionals to investigate Diels-Alder reactions quantitatively. After confirming that LC-DFT accurately reproduces the orbital energies of the reactant and product molecules of the Diels-Alder reactions, the global hardness responses, the halves of highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, along the intrinsic reaction coordinates of two Diels-Alder reactions were computed. We noticed that LC-DFT results satisfy the maximum hardness rule for overall reaction paths while conventional functionals violate this rule on the reaction pathways. Furthermore, our results also show that the HOMO-LUMO gap variations are close to the reaction enthalpies for these Diels-Alder reactions. Based on these results, we foresee quantitative reaction analysis on the orbital energies. Copyright © 2012 Wiley Periodicals, Inc.

Super-multi-nucleon transfer observed in 60Ni+124Sn reaction slightly above the barrier

International Nuclear Information System (INIS)

Tomasi, E.; Pravikoff, M.S.; Nolte, E.; Morinaga, H.

1982-01-01

In order to investigate the behaviour of nucleon transfer near the Coulomb barrier through the produced radioactivities, we have studied the 60 Ni+ 124 Sn system, the residual activity measurements were done at three lab energies of 237, 247 and 258 MeV (Bsub(c)(lab) = 234 MeV). For the highest energy we measured also the angular distribution. In addition to activities corresponding to a few nucleon transfers and evaporation residues, a large number of radioactive nuclei was found, which could be attributed to another class of reaction mechanism. Here, we report on this new phenomenon, which might be due to a super-multi-nucleon transfer, on the basis of the measured angular and mass distributions

Molecular biology - Part I: Techniques, terminology, and concepts

International Nuclear Information System (INIS)

Brown, J. Martin

1996-01-01

Purpose/Objective: One of the barriers to understanding modern molecular biology is the lack of a clear understanding of the relevant terminology, techniques, and concepts. This refresher course is intended to address these deficiencies starting from a basic level. The lecture will cover many of the common uses of recombinant DNA, including gene cloning and manipulation. The goal is to enable the nonspecialist to increase his or her understanding of molecular biology in order to more fully enjoy reading current publications and/or listening seminars. Radiation biologists trying to understand a little more molecular biology should also benefit. The following concepts will be among those explained and illustrated: restriction endonucleases, gel electrophoresis, gene cloning, use of vectors such as plasmids, bacteriophage, cosmids and viruses, cDNA and genomic libraries, Southern, Northern, and Western blotting, fluorescent in situ hybridization, polymerase chain reaction (PCR), gel retardation, and reporter gene assays

Heterogeneous reactions of dioctahedral smectites in illite-smectite and kaolinite-smectite mixed-layers: applications to clay materials for engineered barriers

International Nuclear Information System (INIS)

Meunier, A.; Proust, D.; Beaufort, D.; Lajudie, A.; Petit, J.-C.

1992-01-01

The clay materials selected for use in the engineered barriers of the French nuclear waste isolation programme are mainly composed of dioctahedral smectite, either bentonite of Wyoming type or kaolinite-smectites most often consist of randomly stacked layers with low and high charges. In the case of the Wyoming-type bentonite, these two differently charged layers do not react in the same way when subjected to hydrothermal alteration. Overall, the low-charge smectite layers react to form high-charge smectite layers + quartz + kaolinite. Then, fixing K ions, the high-charge smectite layers are transformed into illite-smectite mixed-layers (I/S) when the temperature conditions increase. A symmetrical process is observed in natural or experimental hydrothermal conditions when the high-charge smectite layers of I/S minerals react with quartz and/or kaolinite to produce low-charge smectite layers. The chemical properties of the bentonite-engineered barriers clearly depend on the low charge/high charge smectite layer proportion, which is in turn controlled by the temperature-dependent reactions in the vicinity of the waste disposal. Although there are fewer published data on the kaolinite-smectite mixed-layered minerals (K/S), a similar low charge-high charge reaction appears to affect their smectite component. The experimental alteration of K/S leads to the formation of a low-charge beidellite with an increase in the cation-exchange capacity and in the expandability of the clay material. Thus, the properties of the engineered barrier seems to be improved after hydrothermal alteration. (Author)

Single-Molecule Sensing with Nanopore Confinement: from Chemical Reactions to Biological Interactions.

Science.gov (United States)

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing which help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this concept, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

TRIMOLECULAR REACTIONS OF URANIUM HEXAFLUORIDE WITH WATER

Energy Technology Data Exchange (ETDEWEB)

Westbrook, M.; Becnel, J.; Garrison, S.

2010-02-25

The hydrolysis reaction of uranium hexafluoride (UF{sub 6}) is a key step in the synthesis of uranium dioxide (UO{sub 2}) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF{sub 6} molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizeable barrier of 78.2 kJ {center_dot} mol{sup -1}, indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO{sub 2} product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF{sub 6} molecules and one water molecule, and (2) the reaction of two water molecules with a single UF{sub 6} molecule. The predicted reaction of two UF{sub 6} molecules with one water molecule displays an interesting 'fluorine-shuttle' mechanism, a significant energy barrier of 69.0 kJ {center_dot} mol{sup -1} to the formation of UF{sub 5}OH, and an enthalpy of reaction ({Delta}H{sub 298}) of +17.9 kJ {center_dot} mol{sup -1}. The reaction of a single UF{sub 6} molecule with two water molecules displays a 'proton-shuttle' mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ {center_dot} mol{sup -1} and an exothermic enthalpy of reaction ({Delta}H{sub 298}) of -13.9 kJ {center_dot} mol{sup -1}. The exothermic nature of the overall UF{sub 6} + 2 {center_dot} H{sub 2}O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging; however, the sizable energy barrier indicates further study of the UF{sub 6} hydrolysis reaction

Biological intrusion of low-level-waste trench covers

Science.gov (United States)

Hakonson, T. E.; Gladney, E. S.

The long-term integrity of low-level waste shallow land burialsites is dependent on the interaction of physical, chemical, and biological factors that modify the waste containment system. The need to consider biological processes as being potentially important in reducing the integrity of waste burial site cover treatment is demonstrated. One approach to limiting biological intrusion through the waste cover is to apply a barrier within the profile to limit root and animal penetration with depth. Experiments in the Los Alamos Experimental Engineered Test Facility were initiated to develop and evaluate biological barriers that are effective in minimizing intrusion into waste trenches. The experiments that are described employ four different candidate barrier materials of geologic origin. Experimental variables that will be evaluated, in addition to barrier type, are barrier depth and sil overburden depth.

Mathematical biology

CERN Document Server

Murray, James D

1993-01-01

The book is a textbook (with many exercises) giving an in-depth account of the practical use of mathematical modelling in the biomedical sciences. The mathematical level required is generally not high and the emphasis is on what is required to solve the real biological problem. The subject matter is drawn, e.g. from population biology, reaction kinetics, biological oscillators and switches, Belousov-Zhabotinskii reaction, reaction-diffusion theory, biological wave phenomena, central pattern generators, neural models, spread of epidemics, mechanochemical theory of biological pattern formation and importance in evolution. Most of the models are based on real biological problems and the predictions and explanations offered as a direct result of mathematical analysis of the models are important aspects of the book. The aim is to provide a thorough training in practical mathematical biology and to show how exciting and novel mathematical challenges arise from a genuine interdisciplinary involvement with the biosci...

A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

Science.gov (United States)

Chen, Lin; Yueming, Li

2018-06-01

In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

Nuclear dynamics around the barrier: from fusion to evaporation

International Nuclear Information System (INIS)

Simenel, Cedric

2003-01-01

This work is devoted to aspects of nuclear dynamics around the barrier. It is shown that for fusion reactions, the Coulomb field couples relative motion of nuclei to rotation of a deformed projectile independently of the energy and the charge of the nuclei. An experimental study of the reaction 6 He + 190 Os via gamma spectroscopy of product nuclei has shown that the break up of the 6 He is coupled to the relative motion too, a strong hindrance resulting in the fusion around and above the fusion barrier. The path to fusion after overcoming the barrier, especially the charge equilibration, have been studied in the framework of the TDHF theory via the preequilibrium GDR excited in N/Z asymmetric reactions. An application to formation of the super-heavy elements has been proposed. Finally, couplings between protons and neutrons have been shown up in mean field calculations. Their main expected effect is an emission of protons under the Coulomb barrier. (author)

Reaction of long-lived radicals and vitamin C in γ-irradiated mammalian cells and their model system at 295 K. Tunneling reaction in biological system

International Nuclear Information System (INIS)

Matsumoto, Takuro; Miyazaki, Tetsuo; Kosugi, Yoshio; Kumada, Takayuki; Koyama, Sinji; Kodama, Seiji; Watanabe, Masami.

1996-01-01

When golden hamster embryo (GHE) cells or concentrated albumin solution (0.1 kg dm -3 ) that is a model system of cells is irradiated with γ-rays at 295 K, organic radicals produced can be observed by ESR. The organic radicals survive at both 295 K and 310 K for such a long time as 20 hr. The long-lived radicals in GHE cells and the albumin solution react with vitamin C by the rate constants of 0.007 dm 3 mol -1 s -1 and 0.014 dm 3 mol -1 s -1 , respectively. The long-lived radicals in human cells cause gene mutation, which is suppressed by addition of vitamin C. The isotope effect on the rate constant (k) for the reaction of the long-lived radicals and vitamin C has been studied in the albumin solution by use of protonated vitamin C and deuterated vitamin C. The isotope effect (k H /k D ) was more than 20-50 and was interpreted in terms of tunneling reaction. When GHE cells or the aqueous albumin solution (0.1 kg dm -3 ) is irradiated with γ-rays at 295 K, organic radicals produced survive for more than 24 hr at room temperature. Very recently we have found that vitamin C reacts with the long-lived organic radicals in the γ-irradiated albumin solution at high concentration of 0.1 kg dm -3 by the rate constant of 0.014 dm 3 mol -1 s -1 . Since most of reactions in biological systems including the reaction of vitamin C are a transfer of a hydrogen atom or a proton that has a large wave character, it is generally expected that the tunneling reaction may play an important role in biological systems at room temperature. The studies of isotope effects on reactions will give an information on the contribution of tunneling reaction. (J.P.N.)

"Toward High School Biology": Helping Middle School Students Understand Chemical Reactions and Conservation of Mass in Nonliving and Living Systems

Science.gov (United States)

Herrmann-Abell, Cari F.; Koppal, Mary; Roseman, Jo Ellen

2016-01-01

Modern biology has become increasingly molecular in nature, requiring students to understand basic chemical concepts. Studies show, however, that many students fail to grasp ideas about atom rearrangement and conservation during chemical reactions or the application of these ideas to biological systems. To help provide students with a better…

Coupled modelling (transport-reaction) of the fluid-clay interactions and their feed back on the physical properties of the bentonite engineered clay barrier system

International Nuclear Information System (INIS)

Marty, N.

2006-11-01

The originality of this work is to process feed back effects of mineralogical and chemical modifications of clays, in storage conditions, on their physical properties and therefore on their transport characteristics (porosity, molecular diffusion, permeability). These feed back effects are modelled using the KIRMAT code (Kinetic of Reaction and MAss Transfer) developed from the kinetic code KINDIS by adding the effect of water renewal in the mineral-solution reactive cells. KIRMAT resolves mass balance equations associated with mass transport together with the geochemical reactions in a 1D approach. After 100 000 years of simulated interaction at 100 C, with the fluid of the Callovo-Oxfordian geological level (COX) and with iron provided by the steel overpack corrosion, the montmorillonite of the clay barrier is only partially transformed (into illite, chlorite, saponite...). Only outer parts of the modelled profile seem to be significantly affected by smectite dissolution processes, mainly at the interface with the geological environment. The modifications of physical properties show a closure of the porosity at the boundaries of the barrier, by creating a decrease of mass transport by molecular diffusion, essentially at the interface with the iron. Permeability laws applied to this system show a decrease of the hydraulic conductivity correlated with the porosity evolution. Near the COX, the swelling pressure of the clays from the barrier decreases. In the major part of the modelled profile, the engineered clay barrier system seems to keep its initial physical properties (porosity, molecular diffusion, permeability, swelling pressure) and functionalities. (author)

Control of BTEX migration using a biologically enhanced permeable barrier

International Nuclear Information System (INIS)

Borden, R.C.; Goin, R.T.; Kao, C.M.

1997-01-01

A permeable barrier system, consisting of a line of closely spaced wells, was installed perpendicular to ground water flow to control the migration of a dissolved hydrocarbon plume. The wells were charged with concrete briquets that release oxygen and nitrate at a controlled rate, enhancing aerobic biodegradation in the downgradient aquifer. Laboratory batch reactor experiments were conducted to identify concrete mixtures that slowly released oxygen over an extended time period. A full-scale permeable barrier system using ORC was constructed at a gasoline-spill site. During the first 242 days of operation, total BTEX decreased from 17 to 3.4 mg/L and dissolved oxygen increased from 0.4 to 1.8 mg/L during transport through the barrier. Over time, BTEX treatment efficiencies declined, indicating the barrier system had become less effective in releasing oxygen and nutrients to the highly contaminated portion of the aquifer. Point dilution tests and sediment analyses performed at the conclusion of the project indicated that the aquifer in the vicinity of the remediation wells had been clogged by precipitation with iron minerals

Fusion enhancement in the reactions of neutron-rich nuclei

International Nuclear Information System (INIS)

Bian Baoan; Zhang Fengshou; Zhou Hongyu

2009-01-01

The neutron-rich fusion reactions are investigated systematically using the improved isospin dependent quantum molecular dynamics model. By studying the systematic dependence of fusion barrier on neuron excess, we find the enhancement of the fusion cross sections for neutron-rich nuclear reactions that give the lowered static Coulomb barriers. The calculated fusion cross sections agree quantitatively with the experimental data. We further discuss the mechanism of the fusion enhancement of the cross sections for neutron-rich nuclear reactions by analyzing the dynamical lowering of the Coulomb barrier that is attributed to the enhancement of the N/Z ratio at the neck region.

Fusion and reactions of exotic nuclei

Directory of Open Access Journals (Sweden)

Sánchez-Benítez A.M.

2011-10-01

Full Text Available Close to the drip lines, the scattering cross sections of halo nuclei show a different behaviour as compared to the tightly bound projectiles of the stability line. Several experiments carried out in the last decade have been dedicated to investigate the competition between transfer, breakup and fusion channels at energies around and below the Coulomb barrier. The rather complex scenario gives rise to conflicting conclusions concerning the effect of breakup and transfer on reaction dynamics and the sub-barrier fusion process. In this work we discuss recent experimental findings in fusion and reactions of 6He halo nucleus at energies around the Coulomb barrier.

Stochastic simulation of biological reactions, and its applications for studying actin polymerization.

Science.gov (United States)

Ichikawa, Kazuhisa; Suzuki, Takashi; Murata, Noboru

2010-11-30

Molecular events in biological cells occur in local subregions, where the molecules tend to be small in number. The cytoskeleton, which is important for both the structural changes of cells and their functions, is also a countable entity because of its long fibrous shape. To simulate the local environment using a computer, stochastic simulations should be run. We herein report a new method of stochastic simulation based on random walk and reaction by the collision of all molecules. The microscopic reaction rate P(r) is calculated from the macroscopic rate constant k. The formula involves only local parameters embedded for each molecule. The results of the stochastic simulations of simple second-order, polymerization, Michaelis-Menten-type and other reactions agreed quite well with those of deterministic simulations when the number of molecules was sufficiently large. An analysis of the theory indicated a relationship between variance and the number of molecules in the system, and results of multiple stochastic simulation runs confirmed this relationship. We simulated Ca²(+) dynamics in a cell by inward flow from a point on the cell surface and the polymerization of G-actin forming F-actin. Our results showed that this theory and method can be used to simulate spatially inhomogeneous events.

Stochastic simulation of biological reactions, and its applications for studying actin polymerization

International Nuclear Information System (INIS)

Ichikawa, Kazuhisa; Suzuki, Takashi; Murata, Noboru

2010-01-01

Molecular events in biological cells occur in local subregions, where the molecules tend to be small in number. The cytoskeleton, which is important for both the structural changes of cells and their functions, is also a countable entity because of its long fibrous shape. To simulate the local environment using a computer, stochastic simulations should be run. We herein report a new method of stochastic simulation based on random walk and reaction by the collision of all molecules. The microscopic reaction rate P r is calculated from the macroscopic rate constant k. The formula involves only local parameters embedded for each molecule. The results of the stochastic simulations of simple second-order, polymerization, Michaelis–Menten-type and other reactions agreed quite well with those of deterministic simulations when the number of molecules was sufficiently large. An analysis of the theory indicated a relationship between variance and the number of molecules in the system, and results of multiple stochastic simulation runs confirmed this relationship. We simulated Ca 2+ dynamics in a cell by inward flow from a point on the cell surface and the polymerization of G-actin forming F-actin. Our results showed that this theory and method can be used to simulate spatially inhomogeneous events

Ex Vivo Antioxidant Activity of Selected Medicinal Plants against Fenton Reaction-Mediated Oxidation of Biological Lipid Substrates

Directory of Open Access Journals (Sweden)

Namratha Pai Kotebagilu

2015-01-01

Full Text Available Free radical-mediated oxidation is often linked to various degenerative diseases. Biological substrates with lipids as major components are susceptible to oxygen-derived lipid peroxidation due to their composition. Lipid peroxide products act as biomarkers in evaluating the antioxidant potential of various plants and functional foods. The study focused on evaluation of the antioxidant potential of two extracts (methanol and 80% methanol of four medicinal plants, Andrographis paniculata, Costus speciosus, Canthium parviflorum, and Abrus precatorius, against Fenton reaction-mediated oxidation of three biological lipid substrates; cholesterol, low-density lipoprotein, and brain homogenate. The antioxidant activity of the extracts was measured by thiobarbituric acid reactive substances method. Also, the correlation between the polyphenol, flavonoid content, and the antioxidant activity in biological substrates was analyzed. Results indicated highest antioxidant potential by 80% methanol extract of Canthium parviflorum (97.55%, methanol extract of Andrographis paniculata (72.15%, and methanol extract of Canthium parviflorum (49.55% in cholesterol, low-density lipoprotein, and brain, respectively. The polyphenol and flavonoid contents of methanol extract of Andrographis paniculata in cholesterol (r=0.816 and low-density lipoprotein (r=0.948 and Costus speciosus in brain (r=0.977, polyphenols, and r=0.949, flavonoids correlated well with the antioxidant activity. The findings prove the antioxidant potential of the selected medicinal plants against Fenton reaction in biological lipid substrates.

Fusion barrier distributions and fission anisotropies

International Nuclear Information System (INIS)

Hinde, D.J.; Morton, C.R.; Dasgupta, M.; Leigh, J.R.; Lestone, J.P.; Lemmon, R.C.; Mein, J.C.; Newton, J.O.; Timmers, H.; Rowley, N.; Kruppa, A.T.

1995-01-01

Fusion excitation functions for 16,17 O+ 144 Sm have been measured to high precision. The extracted fusion barrier distributions show a double-peaked structure interpreted in terms of coupling to inelastic collective excitations of the target. The effect of the positive Q-value neutron stripping channel is evident in the reaction with 17 O. Fission and evaporation residue cross-sections and excitation functions have been measured for the reaction of 16 O+ 208 Pb and the fusion barrier distribution and fission anisotropies determined. It is found that the moments of the fusion l-distribution determined from the fusion and fission measurements are in good agreement. ((orig.))

Study of the dynamical potential barriers in heavy ion collisions

International Nuclear Information System (INIS)

Zhu, Long; Su, Jun; Xie, Wen-Jie; Zhang, Feng-Shou

2013-01-01

The nucleus–nucleus interaction potentials for the fusion reactions 16 O + 208 Pb, 64 Ni + 64 Ni, 58 Ni + 58 Ni and 16 O + 154 Sm are extracted from the improved isospin-dependent quantum molecular dynamics model. The shell correction effects are discussed. The negative shell correction energies lower potential barriers of a certain reaction. The incident energy dependence of the potential barrier is investigated for each system. A complex phenomenon of energy dependence is observed. It is also found that incident energy dependence of the barrier radius and barrier height shows opposite behaviors. The Coulomb potential shows weak energy dependence when distance of two colliding nuclei is lower than the touching distance. The isospin effects of the potential barrier are investigated. The orientation effects of the potential barrier is also discussed for the system 16 O + 154 Sm. The fusion cross sections that correspond to the equatorial orientation of 154 Sm are very low in sub-barrier region because of the high fusion barriers and the shallow potential pockets

Theoretical studies of the reactions of HCN with atomic hydrogen

International Nuclear Information System (INIS)

Bair, R.A.; Dunning, T.H. Jr.

1985-01-01

A comprehensive theoretical study has been made of the energetics of the important pathways involved in the reaction of hydrogen atoms with hydrogen cyanide. For each reaction ab initio GVB-CI calculations were carried out to determine the structures and vibrational frequencies of the reactants, transition states, and products; then POL-CI calculations were carried out to more accurately estimate the electronic contribution to the energetics of the reactions. The hydrogen abstraction reaction is calculated to be endoergic by 24 kcal/mol [expt. ΔH (0 K) = 16--19 kcal/mol] with a barrier of 31 kcal/mol in the forward direction and 6 kcal/mol in the reverse direction. For the hydrogen addition reactions, addition to the carbon atom is calculated to be exoergic by 19 kcal/mol with a barrier of 11 kcal/mol, while addition to the nitrogen center is essentially thermoneutral with a barrier of 17 kcal/mol. Calculations were also carried out on the isomerization reactions of the addition products. The cis→trans isomerization of HCNH has a barrier of only 10 kcal/mol with the trans isomer being more stable by 5 kcal/mol. The (1,2)-hydrogen migration reaction, converting H 2 CN to trans-HCNH, is endoergic by only 14 kcal/mol, but the calculated barrier for the transfer is 52 kcal/mol. The energy of the migration pathway thus lies above that of the dissociation--recombination pathway

Dynamics of Db isotopes formed in reactions induced by 238U, 248Cm, and 249Bk across the Coulomb barrier

Science.gov (United States)

Kaur, Gurjit; Sandhu, Kirandeep; Kaur, Amandeep; Sharma, Manoj K.

2018-05-01

The dynamical cluster decay model is employed to investigate the decay of *265Db and *267Db nuclei, formed in the 27Al+238U , 18O+249Bk , and 19F+248Cm hot fusion reactions at energies around the Coulomb barrier. First, the fission dynamics of the 27Al+238U reaction is explored by investigating the fragmentation and preformation yield of the reaction. The symmetric mass distribution of the fission fragments is observed for *265Db nucleus, when static β2 i deformations are used within hot optimum orientation approach. However, the mass split gets broaden for the use of β2 i-dynamical hot configuration of the fragments and becomes clearly asymmetric for the cold-static-deformed approach. Within the application of cold orientations of fragments, a new fission channel is observed at mass asymmetry η =0.29 . In addition to 238U-induced reaction, the work is carried out to address the fission and neutron evaporation cross sections of *267Db nucleus formed via 19F+248Cm and 18O+249Bk reactions, besides a comprehensive analysis of fusion and capture processes. Higher fusion cross sections and compound nucleus formation probabilities (PCN) are obtained for the 18O+249Bk reaction, as larger mass asymmetry in the entrance channel leads to reduced Coulomb factor. Finally, the role of sticking (IS) and nonsticking (INS) moments of inertia is analyzed for the 4 n and 5 n channels of *267Db nuclear system.

Fuzzy barrier distributions

International Nuclear Information System (INIS)

Piasecki, E.

2009-01-01

Heavy-ion collisions often produce a fusion barrier distribution with structures displaying a fingerprint of couplings to highly collective excitations [1]. Basically the same distribution can be obtained from large-angle quasi-elastic scattering, though here the role of the many weak direct-reaction channels is unclear. For 2 0N e + 9 0Z r we have observed the barrier structures expected for the highly deformed neon projectile, but for 2 0N e + 9 2Z r we find completely smooth distribution (see Fig.1). We find that transfer channels in these systems are of similar strength but single particle excitations are significantly stronger in the latter case. They apparently reduce the 'resolving power' of the quasi-elastic channel, what leads to smeared out, or 'fuzzy' barrier distribution. This is the first case when such a phenomenon has been observed.(author)

The fate of nanocarriers as nanomedicines in vivo: important considerations and biological barriers to overcome.

Science.gov (United States)

Moros, M; Mitchell, S G; Grazú, V; de la Fuente, J M

2013-01-01

Many pharmaceuticals on the market suffer from two significant limitations to their activity: lack of specificity toward the pathological site and poor aqueous solubility. Both factors therefore require the application of a large total dose of a drug to achieve high local concentration, causing numerous off-target toxic effects. Consequently, the grand aim of targeted drug delivery - the often-referred "magic bullet" - promises to improve drug concentration at the target site and maximize therapeutic response. Nanomaterial drug delivery systems have been explored extensively in the recent years for just this purpose. In the field of medicine, nanocarriers (NCs) have the potential to improve the biodistribution and pharmacokinetic characteristics of drugs, thereby reducing side effects while improving the therapeutic effect of drugs. Many nanomaterials are exquisitely designed and possess potent properties, yet it is extremely important to note that a general understanding of the interaction of nanomaterials with biological systems is essential for any such model properties to be effective in vivo, since the body presents a host of biological 'barriers' that will be encountered drug NCs. This review offers a general overview of the different biological obstacles that a NC must negotiate before it can carry out its desired role as a medicinal agent. From this standpoint we suggest aspects that should be considered for the rational design of novel nanomaterials possessing physicochemical properties that are appropriate for therapeutic or theragnostic applications.

Role amplification of the coulomb interaction in nuclear reactions

Energy Technology Data Exchange (ETDEWEB)

Kumar, Ashok; Soni, S K; Pancholi, S K; Gupta, S L [AN SSSR, Moscow. Radiotekhnicheskij Inst.

1976-10-01

The genarally adopted estimate of coulomb interaction in nuclear reactions based on the comparison of relative energies of real particles participating in the reaction with the coulomb barrier has been shown to provide wrong presentation of the role of coulomb interaction in the reaction mechanism. The relative energy of particles participating in virtual processes forming the reaction mechanism and its relation to the coulomb barrier turn out to be tens of per cent less than for the particles in an inlet channel. This is the main reason of increasing the role of coulomb interaction in the reaction mechanism. This increase is particularly significant for nuclei with large charges, in particular, in heavy ion reaction.

Organometallic copper I, II or III species in an intramolecular dechlorination reaction

KAUST Repository

Poater, Albert

2013-03-15

The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.

Metal-free bioconjugation reactions.

Science.gov (United States)

van Berkel, Sander S; van Delft, Floris L

2013-01-01

The recent strategy to apply chemical reactions to address fundamental biological questions has led to the emergence of entirely new conjugation reactions that are fast and irreversible, yet so mild and selective that they can be performed even in living cells or organisms. These so-called bioorthogonal reactions open novel avenues, not only in chemical biology research, but also in many other life sciences applications, including the modulation of biopharmaceuticals by site-specific modification approaches.

Biological intrusion of low-level-waste trench covers

International Nuclear Information System (INIS)

Hakonson, T.E.; Gladney, E.S.

1981-01-01

The long-term integrity of low-level waste shallow land burial sites is dependent on the interaction of physical, chemical, and biological factors that modify the waste containment system. Past research on low-level waste shallow land burial methods has emphasized physical (i.e., water infiltration, soil erosion) and chemical (radionuclide leaching) processes that can cause waste site failure and subsequent radionuclide transport. The purpose of this paper is to demonstrate the need to consider biological processes as being potentially important in reducing the integrity of waste burial site cover treatments. Plants and animals not only can transport radionuclides to the ground surface via root systems and soil excavated from the cover profile by animal burrowing activities, but they modify physical and chemical processes within the cover profile by changing the water infiltration rates, soil erosion rates and chemical composition of the soil. One approach to limiting biological intrusion through the waste cover is to apply a barrier within the profile to limit root and animal penetration with depth. Experiments in the Los Alamos Experimental Engineered Test Facility were initiated to develop and evaluate biological barriers that are effective in minimizing intrusion into waste trenches. The experiments that are described employ four different candidate barrier materials of geologic origin. Experimental variables that will be evaluated, in addition to barrier type, are barrier depth and soil overburden depth. The rate of biological intrusion through the various barrier materials is being evaluated through the use of activatable stable tracers

[Cycloferon biological activity characteristics].

Science.gov (United States)

Utkina, T M; Potekhina, L P; Kartashova, O L; Vasilchenko, A S

2014-01-01

Study the effect of cycloferon in experimental and clinical conditions on persistence properties of aurococci as well as features of their morpho-functional reaction by atomic force microscopy. The study was carried out in 12 Staphylococcus aureus clones isolated from mucous membrane of nose anterior part of a resident carrier. The effect of cycloferon in vivo was evaluated in 26 resident staphylococci carriers under the control of anti-carnosine activity of staphylococci. Anti-carnosine activity was determined by O.V. Bukharin et al. (1999), biofilm formation -by G.A. O'Toole et al. (2000). Staphylococci treated with cycloferon were studied by atomic force microscopy in contact mode using scanning probe SMM-2000 microscope. The decrease of persistence properties of staphylococci under the effect of cycloferon in vitro and in vivo may be examined as one of the mechanisms of biological activity of the preparation. A significant increase of S. aureus surface roughness and changes in their morphology under the effect of cycloferon allow stating the disorder of barrier functions in the aurococci cell wall. The data obtained expand the understanding of cycloferon biological activity mechanisms.

Liquid-drop effects in sub-barrier fusion reactions

Energy Technology Data Exchange (ETDEWEB)

Aguiar, C E; Barbosa, V C; Canto, L F; Donangelo, R

1988-01-28

We introduce an operational measure for the enhancement of the fusion cross section at sub-barrier energies in terms of an asymptotic energy shift ..delta..E. It is shown that ..delta..E has a continuously growing trend with the size of the system. This trend is explained in terms of neck formation using the liquid-drop model. Deviations from this trend are attributed to strong coupling to specific channels.

On the pH dependence of electrochemical proton transfer barriers

DEFF Research Database (Denmark)

Rossmeisl, Jan; Chan, Karen; Skulason, Egill

2016-01-01

The pH dependence of rate of the hydrogen evolution/oxidation reaction HER/HOR is investigated. Based on thermodynamic considerations, a possible explanation to the low exchange current for hydrogen reactions in alkaline is put forward. We propose this effect to be a consequence of the change...... environment in the double layer region. The entropic barrier can be rate determining only when the surface catalysis is fast. Therefore the effect of pH is most pronounced on good catalysts and for fast reactions. This entropic barrier is also in a good agreement with the unusually low prefactor measured...

Barriers and post-closure monitoring (AL121125)

International Nuclear Information System (INIS)

Bostick, K.V.; Janecky, D.

1995-01-01

This project focuses on the rapid implementation of near-surface barriers, biotreatment, and post-closure monitoring technology. It uses water-permeable and biologic barriers that chemically capture and/or degrade contaminants without significantly altering the natural water flow regime. Barrier approaches are being tested for two different applications. The first is the use of barriers for confinement of chemical contaminants for in-trench treatments with leach systems or an in-place bioreactor. The second is an enhancement of the current practice of emplacing grout or clay slurry walls into direct horizontal surface and subsurface water flows around a contaminated area by integrating permeable reactive barriers and petroleum reservoir gel/foam/polymer technology

Nuclear reorganization barriers to electron transfer

International Nuclear Information System (INIS)

Sutin, N.; Brunschwig, B.S.; Creutz, C.; Winkler, J.R.

1988-01-01

The nuclear barrier to electron transfer arises from the need for reorganization of intramolecular and solvent internuclear distances prior to electron transfer. For reactions with relatively small driving force (''normal'' free-energy region) the nuclear factors and rates increase as intrinsic inner-shell and outer-shell barriers decrease; this is illustrated by data for transition metal complexes in their ground electronic states. By contrast, in the inverted free-energy region, rates and nuclear factors decrease with decreasing ''intrinsic'' barriers; this is illustrated by data for the decay of charge-transfer excited states. Several approaches to the evaluation of the outer-shell barrier are explored in an investigation of the distance dependence of the nuclear factor in intramolecular electron-transfer processes. 39 refs., 14 figs., 3 tabs

Phenomenon of quantum low temperature limit of chemical reaction rates

International Nuclear Information System (INIS)

Gol'danskij, V.I.

1975-01-01

The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerisation, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerisation reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau 0 ) required to add one new link to the polymer chain of formaldehyde during its polymerisation by radiation and during postpolymerisation and to establish that below 80K the increase of tau 0 slows down and that at T approximately equal to 10-4K the time tau 0 reaches a plateau (tau 0 approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life)

Phenomenon of quantum low temperature limit of chemical reaction rates

Energy Technology Data Exchange (ETDEWEB)

Gol' danskii, V I [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1975-12-01

The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life).

Modelling the endothelial blood-CNS barriers: a method for the production of robust in vitro models of the rat blood-brain barrier and blood-spinal cord barrier.

Science.gov (United States)

Watson, P Marc D; Paterson, Judy C; Thom, George; Ginman, Ulrika; Lundquist, Stefan; Webster, Carl I

2013-06-18

Modelling the blood-CNS barriers of the brain and spinal cord in vitro continues to provide a considerable challenge for research studying the passage of large and small molecules in and out of the central nervous system, both within the context of basic biology and for pharmaceutical drug discovery. Although there has been considerable success over the previous two decades in establishing useful in vitro primary endothelial cell cultures from the blood-CNS barriers, no model fully mimics the high electrical resistance, low paracellular permeability and selective influx/efflux characteristics of the in vivo situation. Furthermore, such primary-derived cultures are typically labour-intensive and generate low yields of cells, limiting scope for experimental work. We thus aimed to establish protocols for the high yield isolation and culture of endothelial cells from both rat brain and spinal cord. Our aim was to optimise in vitro conditions for inducing phenotypic characteristics in these cells that were reminiscent of the in vivo situation, such that they developed into tight endothelial barriers suitable for performing investigative biology and permeability studies. Brain and spinal cord tissue was taken from the same rats and used to specifically isolate endothelial cells to reconstitute as in vitro blood-CNS barrier models. Isolated endothelial cells were cultured to expand the cellular yield and then passaged onto cell culture inserts for further investigation. Cell culture conditions were optimised using commercially available reagents and the resulting barrier-forming endothelial monolayers were characterised by functional permeability experiments and in vitro phenotyping by immunocytochemistry and western blotting. Using a combination of modified handling techniques and cell culture conditions, we have established and optimised a protocol for the in vitro culture of brain and, for the first time in rat, spinal cord endothelial cells. High yields of both CNS

Expedient construction of small molecule macroarrays via sequential palladium- and copper-mediated reactions and their ex situ biological testing.

Science.gov (United States)

Frei, Reto; Breitbach, Anthony S; Blackwell, Helen E

2012-05-01

We report the highly efficient syntheses of a series of focused libraries in the small molecule macroarray format using Suzuki-Miyaura and copper-catalyzed azide-alkyne cycloaddition (or "click") reactions. The libraries were based on stilbene and triazole scaffolds, which are known to have a broad range of biological activities, including quorum-sensing (QS) modulation in bacteria. The library products were generated in parallel on the macroarray in extremely short reaction times (~10-20 min) and isolated in excellent purities. Biological testing of one macroarray library post-cleavage (ex situ) revealed several potent agonists of the QS receptor, LuxR, in Vibrio fischeri. These synthetic agonists, in contrast to others that we have reported, were only active in the presence of the native QS signal in V. fischeri, which is suggestive of a different mode of activity. Notably, the results presented herein showcase the ready compatibility of the macroarray platform with chemical reactions that are commonly utilized in small molecule probe and drug discovery today. As such, this work serves to expand the utility of the small molecule macroarray as a rapid and operationally straightforward approach toward the synthesis and screening of bioactive agents.

Student Research in Rocket and Plume-Reaction Kinetics

National Research Council Canada - National Science Library

Fontijn, Arthur

1998-01-01

Semi-empirical configuration interaction (SECI) theory has been extended to predict activation barriers for combustion reactions of boron group halide oxidation reactions, Good agreement with experiments has been obtained...

Reactive Membrane Barriers for Containment of Subsurface Contamination

Energy Technology Data Exchange (ETDEWEB)

William A. Arnold; Edward L. Cussler

2007-02-26

The overall goal of this project was to develop reactive membrane barriers--a new and flexible technique to contain and stabilize subsurface contaminants. Polymer membranes will leak once a contaminant is able to diffuse through the membrane. By incorporating a reactive material in the polymer, however, the contaminant is degraded or immobilized within the membrane. These processes increase the time for contaminants to breakthrough the barrier (i.e. the lag time) and can dramatically extend barrier lifetimes. In this work, reactive barrier membranes containing zero-valent iron (Fe{sup 0}) or crystalline silicotitanate (CST) were developed to prevent the migration of chlorinated solvents and cesium-137, respectively. These studies were complemented by the development of models quantifying the leakage/kill time of reactive membranes and describing the behavior of products produced via the reactions within the membranes. First, poly(vinyl alcohol) (PVA) membranes containing Fe{sup 0} and CST were prepared and tested. Although PVA is not useful in practical applications, it allows experiments to be performed rapidly and the results to be compared to theory. For copper ions (Cu{sup 2+}) and carbon tetrachloride, the barrier was effective, increasing the time to breakthrough over 300 times. Even better performance was expected, and the percentage of the iron used in the reaction with the contaminants was determined. For cesium, the CST laden membranes increased lag times more than 30 times, and performed better than theoretical predictions. A modified theory was developed for ion exchangers in reactive membranes to explain this result. With the PVA membranes, the effect of a groundwater matrix on barrier performance was tested. Using Hanford groundwater, the performance of Fe{sup 0} barriers decreased compared to solutions containing a pH buffer and high levels of chloride (both of which promote iron reactivity). For the CST bearing membrane, performance improved by a

Reactive Membrane Barriers for Containment of Subsurface Contamination

International Nuclear Information System (INIS)

William A. Arnold; Edward L. Cussler

2007-01-01

The overall goal of this project was to develop reactive membrane barriers--a new and flexible technique to contain and stabilize subsurface contaminants. Polymer membranes will leak once a contaminant is able to diffuse through the membrane. By incorporating a reactive material in the polymer, however, the contaminant is degraded or immobilized within the membrane. These processes increase the time for contaminants to breakthrough the barrier (i.e. the lag time) and can dramatically extend barrier lifetimes. In this work, reactive barrier membranes containing zero-valent iron (Fe 0 ) or crystalline silicotitanate (CST) were developed to prevent the migration of chlorinated solvents and cesium-137, respectively. These studies were complemented by the development of models quantifying the leakage/kill time of reactive membranes and describing the behavior of products produced via the reactions within the membranes. First, poly(vinyl alcohol) (PVA) membranes containing Fe 0 and CST were prepared and tested. Although PVA is not useful in practical applications, it allows experiments to be performed rapidly and the results to be compared to theory. For copper ions (Cu 2+ ) and carbon tetrachloride, the barrier was effective, increasing the time to breakthrough over 300 times. Even better performance was expected, and the percentage of the iron used in the reaction with the contaminants was determined. For cesium, the CST laden membranes increased lag times more than 30 times, and performed better than theoretical predictions. A modified theory was developed for ion exchangers in reactive membranes to explain this result. With the PVA membranes, the effect of a groundwater matrix on barrier performance was tested. Using Hanford groundwater, the performance of Fe 0 barriers decreased compared to solutions containing a pH buffer and high levels of chloride (both of which promote iron reactivity). For the CST bearing membrane, performance improved by a factor of three when

Quantifying electron transfer reactions in biological systems

DEFF Research Database (Denmark)

Sjulstok, Emil Sjulstok; Olsen, Jógvan Magnus Haugaard; Solov'yov, Ilia A

2015-01-01

which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between...

Hydrogen transfer reactions of interstellar Complex Organic Molecules

Science.gov (United States)

Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

2018-06-01

Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents.

Science.gov (United States)

Dzhioev, Alan A; Kosov, Daniel S; von Oppen, Felix

2013-04-07

We present an escape rate theory for current-induced chemical reactions. We use Keldysh nonequilibrium Green's functions to derive a Langevin equation for the reaction coordinate. Due to the out of equilibrium electronic degrees of freedom, the friction, noise, and effective temperature in the Langevin equation depend locally on the reaction coordinate. As an example, we consider the dissociation of diatomic molecules induced by the electronic current from a scanning tunnelling microscope tip. In the resonant tunnelling regime, the molecular dissociation involves two processes which are intricately interconnected: a modification of the potential energy barrier and heating of the molecule. The decrease of the molecular barrier (i.e., the current induced catalytic reduction of the barrier) accompanied by the appearance of the effective, reaction-coordinate-dependent temperature is an alternative mechanism for current-induced chemical reactions, which is distinctly different from the usual paradigm of pumping vibrational degrees of freedom.

Structure information from fusion barriers

Indian Academy of Sciences (India)

Pb, using the coupled reaction channel (CRC) method and correct structure information, have been analysed. The barrier distributions derived from these excitation functions including many of the significant channels are featureless, although these channels have considerable effects on the fusion excitation function.

Emotional Barriers to Successful Reemployment: Implications for Counselors.

Science.gov (United States)

Guindon, Mary H.; Smith, Barrett

2002-01-01

Common responses to job loss include stress reactions, depression and anxiety, and lowered self-esteem. This article describes these common reactions to job loss and unemployment, explains how to recognize their symptoms, and discusses ways counselors can address these emotional barriers to finding meaningful employment. (Contains 50 references.)…

Barrier for cold-fusion production of superheavy elements

International Nuclear Information System (INIS)

Ichikawa, Takatoshi; Iwamoto, Akira; Moeller, Peter; Sierk, Arnold J.

2005-01-01

We estimate the fusion-barrier height B fu (two-body) for approaching ions in cold-fusion reactions in a model where the projectile deformation and quadrupole zero-point vibrational energy are taken into account. This barrier height is defined as the barrier energy at the target and projectile separation distance where an original oblate deformation of projectile and/or target caused by a repulsive Coulomb force turns into a large prolate deformation caused by the attractive nuclear force as the target and projectile come closer. The instability develops before touching because the attractive short-range nuclear force overcomes the repulsive Coulomb force and the shape-stabilizing effect of shell structure. The shell structure of the doubly magic 208 Pb target is sufficiently strong that its shape remains very close to spherical in all cases studied here. The fusion potential for approaching ions in the two-body channel is calculated in the macroscopic-microscopic model with the quadrupole vibrational zero-point energy obtained in the WKB approximation. We compare our results with data from 10 experimental cold-fusion reactions and with the Bass barriers. Differences and similarities between the Yukawa-plus-exponential model and the Bass model are discussed. We also calculate five-dimensional potential-energy surfaces for the single compound system and show that well-established fission and fusion valleys are both present. For heavy systems, B fu (two-body) becomes lower than the fission barrier just beyond the ground state of the compound system. In the vicinity of this transition, the optimum collision energy for formation of evaporation residues can be expected to depend in a delicate fashion on the interplay among B fu (two-body) , the fusion valley, the fission barrier of the compound system, and the one- and two-neutron separation energies S 1n and S 2n . We discuss these issues in detail and calculate fission-barrier heights. Except for reactions in which

Biointrusion test plan for the Permanent Isolation Surface Barrier Prototype

International Nuclear Information System (INIS)

Link, S.O.; Cadwell, L.L.; Brandt, C.A.; Downs, J.L.; Rossi, R.E.; Gee, G.W.

1994-04-01

This document provides a testing and monitoring plan for the biological component of the prototype barrier slated for construction at the Hanford Site. The prototype barrier is an aboveground structure engineered to demonstrate the basic features of an earthen cover system. It is designed to permanently isolate waste from the biosphere. The features of the barrier include multiple layers of soil and rock materials and a low-permeability asphalt sublayer. The surface of the barrier consists of silt loam soil, covered with plants. The barrier sides are reinforced with rock or coarse earthen-fill to protect against wind and water erosion. The sublayers inhibit plant and animal intrusion and percolation of water. A series of tests will be conducted on the prototype barrier over the next several years to evaluate barrier performance under extreme climatic conditions. Plants and animals will play a significant role in the hydrologic and water and wind erosion characteristics of the prototype barrier. Studies on the biological component of the prototype barrier will include work on the initial revegetation of the surface, continued monitoring of the developing plant community, rooting depth and dispersion in the context of biointrusion potential, the role of plants in the hydrology of the surface and toe regions of the barrier, the role of plants in stabilizing the surface against water and wind erosion, and the role of burrowing animals in the hydrology and water and wind erosion of the barrier

Capturing Chemistry in Action with Electrons: Realization of Atomically Resolved Reaction Dynamics.

Science.gov (United States)

Ischenko, Anatoly A; Weber, Peter M; Miller, R J Dwayne

2017-08-23

One of the grand challenges in chemistry has been to directly observe atomic motions during chemical processes. The depiction of the nuclear configurations in space-time to understand barrier crossing events has served as a unifying intellectual theme connecting the different disciplines of chemistry. This challenge has been cast as an imaging problem in which the technical issues reduce to achieving not only sufficient simultaneous space-time resolution but also brightness for sufficient image contrast to capture the atomic motions. This objective has been met with electrons as the imaging source. The review chronicles the first use of electron structural probes to study reactive intermediates, to the development of high bunch charge electron pulses with sufficient combined spatial-temporal resolution and intensity to literally light up atomic motions, as well as the means to characterize the electron pulses in terms of temporal brightness and image reconstruction. The use of femtosecond Rydberg spectroscopy as a novel means to use internal electron scattering within the molecular reference frame to obtain similar information on reaction dynamics is also discussed. The focus is on atomically resolved chemical reaction dynamics with pertinent references to work in other areas and forms of spectroscopy that provide additional information. Effectively, we can now directly observe the far-from-equilibrium atomic motions involved in barrier crossing and categorize chemistry in terms of a power spectrum of a few dominant reaction modes. It is this reduction in dimensionality that makes chemical reaction mechanisms transferrable to seemingly arbitrarily complex (large N) systems, up to molecules as large as biological macromolecules (N > 1000 atoms). We now have a new way to reformulate reaction mechanisms using an experimentally determined dynamic mode basis that in combination with recent theoretical advances has the potential to lead to a new conceptual basis for

Nuclear halo and its related reactions

International Nuclear Information System (INIS)

Zhang Huanqiao

2005-01-01

nuclear halo in terms of the analytical expressions of the expectation value for the operator r 2 in a finite square-well potential. Nuclear reactions induced by halo and weekly bound nuclei are a topic of current interest. We have measured the complete fusion cross sections of 6 Li+ 208 Pb and found the fusion cross sections above the Coulomb barrier are suppressed due to the breakup effects of weekly bound projectile 6 Li. We have also measured the elastic and quasi-elastic excitation functions of 6,7 Li, 9 Be+ 208 Pb, 209 Ri. From these excitation functions, barrier distributions are extracted and compared with the predictions of the coupled-channels model. It is found that the barrier distributions are somehow broaden and shift to lower energies which may be a signature of the breakup effects of the weekly bound projectiles. Gomes et al. study the behavior of the fusion, breakup, reaction, and elastic scattering of different projectiles on 64 Zn at near and above barrier energies. They found that the elastic (noncapture) breakup cross section is important at energies close to and above the Coulomb barrier and increases the reaction cross sections. In addition, they show that the breakup process at near and below barrier energies is responsible for the vanishing of the usual threshold anomaly of the optical and gives rise to a new type of anomaly. Recently, Newton et al. systematically analyzed the high precision fusion cross sections for Z p Z t p Z t 48 Ca+ 90,96 Zr at the XTU Tandem accelerator facility of the Laboratori Nazionali di Legnaro, Italy. The comparison of experimental 40,48 Ca+ 90,96 Zr fusion data shows that fusion of 40 Ca+ 96 Zr is much enhanced due to the positive Q-values of the transfer channels. The much larger enhancement for the 40 Ca+ 96 Zr as compared to other three systems clearly indicates that neutron transfer with the positive Q-value should play a significant role in sub-barrier fusion. In order to extract the information on the complex

Structure Biology of Membrane Bound Enzymes

Energy Technology Data Exchange (ETDEWEB)

Fu, Dax [Johns Hopkins Univ., Baltimore, MD (United States). School of Medicine. Dept. of Physiology

2016-11-30

The overall goal of the proposed research is to understand the membrane-associated active processes catalyzed by an alkane $\\square$-hydroxylase (AlkB) from eubacterium Pseudomonase oleovorans. AlkB performs oxygenation of unactivated hydrocarbons found in crude oils. The enzymatic reaction involves energy-demanding steps in the membrane with the uses of structurally unknown metal active sites featuring a diiron [FeFe] center. At present, a critical barrier to understanding the membrane-associated reaction mechanism is the lack of structural information. The structural biology efforts have been challenged by technical difficulties commonly encountered in crystallization and structural determination of membrane proteins. The specific aims of the current budget cycle are to crystalize AlkB and initiate X-ray analysis to set the stage for structural determination. The long-term goals of our structural biology efforts are to provide an atomic description of AlkB structure, and to uncover the mechanisms of selective modification of hydrocarbons. The structural information will help elucidating how the unactivated C-H bonds of saturated hydrocarbons are oxidized to initiate biodegradation and biotransformation processes. The knowledge gained will be fundamental to biotechnological applications to biofuel transformation of non-edible oil feedstock. Renewable biodiesel is a promising energy carry that can be used to reduce fossil fuel dependency. The proposed research capitalizes on prior BES-supported efforts on over-expression and purification of AlkB to explore the inner workings of a bioenergy-relevant membrane-bound enzyme.

Synthesis and Biological Activity of Some 3, 5-Diarylisoxazoline Derivatives: Reaction of Substituted Chalcones with Hydroxylamine Hydrochloride

Directory of Open Access Journals (Sweden)

Vandana Sharma

2010-01-01

Full Text Available A series of 3-aryl-5-styrylisoxazoline/ 3,5-diarylisoxazoline derivatives were synthesized by the reaction of appropriately substituted chalcones and hydroxylamine hydrochloride in presence of alkali in ethanol. The synthesized heterocycles have been characterized on the basis of their chemical properties and spectroscopic data. These compounds were tested for biological activity against a variety of test organisms

Barrier experiment: Shock initiation under complex loading

Energy Technology Data Exchange (ETDEWEB)

Menikoff, Ralph [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-01-12

The barrier experiments are a variant of the gap test; a detonation wave in a donor HE impacts a barrier and drives a shock wave into an acceptor HE. The question we ask is: What is the trade-off between the barrier material and threshold barrier thickness to prevent the acceptor from detonating. This can be viewed from the perspective of shock initiation of the acceptor subject to a complex pressure drive condition. Here we consider key factors which affect whether or not the acceptor undergoes a shock-to-detonation transition. These include the following: shock impedance matches for the donor detonation wave into the barrier and then the barrier shock into the acceptor, the pressure gradient behind the donor detonation wave, and the curvature of detonation front in the donor. Numerical simulations are used to illustrate how these factors affect the reaction in the acceptor.

Perceived Barriers to the Use of High-Fidelity Hands-On Simulation Training for Contrast Reaction Management: Why Programs are Not Using It.

Science.gov (United States)

Chinnugounder, Sankar; Hippe, Daniel S; Maximin, Suresh; O'Malley, Ryan B; Wang, Carolyn L

2015-01-01

Although subjective and objective benefits of high-fidelity simulation have been reported in medicine, there has been slow adoption in radiology. The purpose of our study was to identify the perceived barriers in the use of high-fidelity hands-on simulation for contrast reaction management training. An IRB exempt 32 questions online web survey was sent to 179 non-military radiology residency program directors listed in the Fellowship and Residency Electronic Interactive Database Access system (FREIDA). Survey questions included the type of contrast reaction management training, cost, time commitment of residents and faculty, and the reasons for not using simulation training. Responses from the survey were summarized as count (percentage), mean ± standard deviation (SD), or median (range). 84 (47%) of 179 programs responded, of which 88% offered CRM training. Most (72%) conducted the CRM training annually while only 4% conducted it more frequently. Didactic lecture was the most frequently used training modality (97%), followed by HFS (30%) and computer-based simulation (CBS) (19%); 5.5% used both HFS and CBS. Of the 51 programs that offer CRM training but do not use HFS, the most common reason reported was insufficient availability (41%). Other reported reasons included cost (33%), no access to simulation centers (33%), lack of trained faculty (27%) and time constraints (27%). Although high-fidelity hands-on simulation training is the best way to reproduce real-life contrast reaction scenarios, many institutions do not provide this training due to constraints such as cost, lack of access or insufficient availability of simulation labs, and lack of trained faculty. As a specialty, radiology needs to better address these barriers at both an institutional and national level. Copyright © 2015 Mosby, Inc. All rights reserved.

Synthesis, molecular docking and biological evaluation as HDAC inhibitors of cyclopeptide mimetics by a tandem three-component reaction and intramolecular [3+2] cycloaddition.

Science.gov (United States)

Pirali, Tracey; Faccio, Valeria; Mossetti, Riccardo; Grolla, Ambra A; Di Micco, Simone; Bifulco, Giuseppe; Genazzani, Armando A; Tron, Gian Cesare

2010-02-01

Novel macrocyclic peptide mimetics have been synthesized by exploiting a three-component reaction and an azide-alkyne [3 + 2] cycloaddition. The prepared compounds were screened as HDAC inhibitors allowing us to identify a new compound with promising biological activity. In order to rationalize the biological results, computational studies have also been performed.

Synthesis and Biological Activity of Some 3,5-Diaryl-1-Benzothiazolopyrazoline Derivatives: Reaction of Chalcones with 2-Hyrazinobenzothiazoles

Directory of Open Access Journals (Sweden)

Vandana Sharma

2009-01-01

Full Text Available A series of 3,5-diaryl-1-benzothiazolopyrazoline derivatives were synthesized by the reaction of appropriately substituted chalcones and 2-hydrazinobenzothiazole in ethanol. The synthesized heterocycles have been characterized on the basis of their chemical properties and spectroscopic data. These compounds were tested for biological activity against a variety of test organisms.

Study of the angular momentum distribution of compound nuclei obtained from fusion reactions close to the Coulomb barrier

International Nuclear Information System (INIS)

Romain, P.

1990-03-01

The effect of the mass asymmetry of the input channel on the compound nuclei spin distribution. The 16 O + 144 Nd and 80 Se + 80 Se reactions produce the same 160 Er compound nucleus in the 38 to 68 MeV energy range. In certain cases, the incident energies required to form the compound nucleus, at the same excitation energies, are very close to the Coulomb barrier. In the experimental device, the 'Chateau de Cristal' multidetector and additional sensors are used. The angular momentum distribution of the different evaporation products are measured by gamma spectrometry techniques. The fusion cross sections are measured by the time-of-flight technique. Theoretical predictions and experimental results concerning the distribution of the compound nucleus angular momentum are compared [fr

Knowledge, perception, practices and barriers of healthcare professionals in Bosnia and Herzegovina towards adverse drug reaction reporting and pharmacovigilance

Directory of Open Access Journals (Sweden)

Maša Amrain

2014-09-01

Full Text Available Introduction: Pharmacovigilance is an arm of patient care. No one wants to harm patients, but unfortunately any medicine will sometimes do just this. Underreporting of adverse drug reactions by healthcare professionals is a major problem in many countries. In order to determine whether our pharmacovigilance system could be improved, and identify reasons for under-reporting, a study to investigate the role of health care professionals in adverse drug reaction (ADR reporting was performed.Methods: A pretested questionnaire comprising of 20 questions was designed for assessment of knowledge, perceptions, practice and barriers toward ADR reporting on a random sample of 1000 healthcare professionals in Bosnia and Herzegovina.Results: Of the 1000 respondents, 870 (87% completed the questionnaire. The survey showed that 62.9% health care professionals would report ADR to the Agency for Medicinal Products and Medical Device of Bosnia and Herzegovina (ALMBIH. Most of surveyed respondents has a positive perception towards ADR reporting, and believes that this is part of their professional and legal obligation, and they also recognize the importance of reporting adverse drug reactions. Only small percent (15.4% of surveyed health care professionals reported adverse drug reaction.Conclusions: The knowledge of ADRs and how to report them is inadequate among health care professionals. Perception toward ADR reporting was positive, but it is not reflected in the actual practice of ADRs, probably because of little experience and knowledge regarding pharmacovigilance. Interventions such as education and training, focusing on the aims of pharmacovigilance, completing the ADR form and clarifying the reporting criteria are strongly recommended.

Quantitative structure-activation barrier relationship modeling for Diels-Alder ligations utilizing quantum chemical structural descriptors.

Science.gov (United States)

Nandi, Sisir; Monesi, Alessandro; Drgan, Viktor; Merzel, Franci; Novič, Marjana

2013-10-30

In the present study, we show the correlation of quantum chemical structural descriptors with the activation barriers of the Diels-Alder ligations. A set of 72 non-catalysed Diels-Alder reactions were subjected to quantitative structure-activation barrier relationship (QSABR) under the framework of theoretical quantum chemical descriptors calculated solely from the structures of diene and dienophile reactants. Experimental activation barrier data were obtained from literature. Descriptors were computed using Hartree-Fock theory using 6-31G(d) basis set as implemented in Gaussian 09 software. Variable selection and model development were carried out by stepwise multiple linear regression methodology. Predictive performance of the quantitative structure-activation barrier relationship (QSABR) model was assessed by training and test set concept and by calculating leave-one-out cross-validated Q2 and predictive R2 values. The QSABR model can explain and predict 86.5% and 80% of the variances, respectively, in the activation energy barrier training data. Alternatively, a neural network model based on back propagation of errors was developed to assess the nonlinearity of the sought correlations between theoretical descriptors and experimental reaction barriers. A reasonable predictability for the activation barrier of the test set reactions was obtained, which enabled an exploration and interpretation of the significant variables responsible for Diels-Alder interaction between dienes and dienophiles. Thus, studies in the direction of QSABR modelling that provide efficient and fast prediction of activation barriers of the Diels-Alder reactions turn out to be a meaningful alternative to transition state theory based computation.

Nuclear structure and fusion at the barrier

International Nuclear Information System (INIS)

Reisdorf, W.

1985-01-01

A comparative study of measured fusion excitation functions in the vicinity of the barrier reveals nuclear structure effects, due in particular to the coupling of the fusion process to direct-reaction channels. (orig.)

Study on fusion potential barrier in heavy ion reactions based on the dynamical model

International Nuclear Information System (INIS)

Tian Junlong; Wu Xizhen; Li Zhuxia; Wang Ning; Liu Fuhu

2004-01-01

Based on an improved quantum molecular dynamics model the static and dynamic potential in the entrance channel of synthesis of superheavy nuclei are studied. The dependence of the static potential (and driving potential) on mass-asymmetry is obtained. From this study authors find out that the mass-symmetric system seems to be difficult to fuse and the fusing system with the largest driving potential could be the optimal choice of the projectile-target combination. By comparing the static potential barrier with the dynamic one authors find that the latter one is lower than former one obviously, and that the dynamical potential barrier is entrance energy dependent. The maximum and minimum of dynamic potential barriers approach to the diabatic (sudden approximation) and the adiabatic static potential barriers, respectively

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

Science.gov (United States)

Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

Barriers to meditation by gender and age among cancer family caregivers.

Science.gov (United States)

Williams, Anna-Leila; Ness, Peter Van; Dixon, Jane; McCorkle, Ruth

2012-01-01

Despite solid basic science research supporting meditation's physiologic benefits, meditation remains a marginalized practice for many Westerners; observational and descriptive studies indicate a spectrum of barriers to meditation practice. The aim of this study was to determine differences in barriers to meditation by gender and age. A cross-sectional survey study of 150 family caregivers to adults with cancer visiting an outpatient chemotherapy center in Connecticut was conducted. The primary outcome was the Determinants of Meditation Practice Inventory. Explanatory variables included demographic characteristics, Center for Epidemiologic Studies-Depression Scale, Big Five Inventory, and Caregiver Reaction Assessment. Participants included 98 women and 52 men. Age range was 18-84 years (M = 52.3 years). The highest frequency of barriers for both genders related to misconceptions about meditation. The total number of barriers to meditation did not significantly vary by gender (p = .10) nor age (p = .27). After adjusting for personality trait, reactions to caregiving, and emotional distress, gender (adjusted β = 0.81, SE = 1.70, p = .63) and age (adjusted β = 0.02, SE = 0.05, p = .67) still did not predict the number of barriers to meditation. Backward elimination in model building showed that personality trait and reactions to caregiving account for 32% of the variability in barriers. The total number of barriers to meditation was examined, and a difference was not found by age or gender. It is possible that differences by age and gender exist at the item level of evaluation but were not evident when evaluating total scores. Further study is needed with samples large enough to have statistical power for item-level analysis.

Unimolecular reaction dynamics of free radicals

International Nuclear Information System (INIS)

Terry A. Miller

2006-01-01

Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy

Finite difference simulation of biological chromium (VI) reduction in ...

African Journals Online (AJOL)

The model results showed that post-barrier infusion of biomass into the clean aquifer downstream of the barrier could be limited by depletion of the substrates within the barrier. The model when fully developed will be used in desktop evaluation of proposed in situ biological barrier systems before implementation in actual ...

Recombination barrier layers in solid-state quantum dot-sensitized solar cells

KAUST Repository

Roelofs, Katherine E.; Brennan, Thomas P.; Dominguez, Juan C.; Bent, Stacey F.

2012-01-01

in situ by successive ion layer adsorption and reaction (SILAR). Aluminum oxide recombination barrier layers were deposited by atomic layer deposition (ALD) at the TiO2/hole-conductor interface. For low numbers of ALD cycles, the Al2O3 barrier layer

Cutaneous reactions in nuclear, biological and chemical warfare

Directory of Open Access Journals (Sweden)

Arora Sandeep

2005-03-01

Full Text Available Nuclear, biological and chemical warfare have in recent times been responsible for an increasing number of otherwise rare dermatoses. Many nations are now maintaining overt and clandestine stockpiles of such arsenal. With increasing terrorist threats, these agents of mass destruction pose a risk to the civilian population. Nuclear and chemical attacks manifest immediately while biological attacks manifest later. Chemical and biological attacks pose a significant risk to the attending medical personnel. The large scale of anticipated casualties in the event of such an occurrence would need the expertise of all physicians, including dermatologists, both military and civilian. Dermatologists are uniquely qualified in this respect. This article aims at presenting a review of the cutaneous manifestations in nuclear, chemical and biological warfare and their management.

Analytical applications of oscillatory chemical reactions: determination of some pharmaceuticaly and biologically important compounds

Directory of Open Access Journals (Sweden)

Pejić Nataša D.

2012-01-01

Full Text Available Novel analytical methods for quantitive determination of analytes based on perturbations of oscillatory chemical reactions realized under open reactor conditions (continuosly fed well stirred tank reactor, CSTR, have been developed in the past twenty years. The proposed kinetic methods are generally based on the ability of the analyzed substances to change the kinetics of the chemical reactions matrix. The unambiguous correlation of quantitative characteristics of perturbations, and the amount (concentration of analyte expressed as a regression equation, or its graphics (calibration curve, enable the determination of the unknown analyte concentration. Attention is given to the development of these methods because of their simple experimental procedures, broad range of linear regression ( 10-7 10-4 mol L-1 and low limits of detection of analytes ( 10-6 10-8 mol L1, in some cases even lower than 10-12 mol L-1. Therefore, their application is very convenient for routine analysis of various inorganic and organic compounds as well as gases. This review summarizes progress made in the past 5 years on quantitative determination of pharmaceutically and biologically important compounds.

Reaction mechanisms of metal complexes

CERN Document Server

Hay, R W

2000-01-01

This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanis...

Investigation of some biologically relevant redox reactions using electrochemical mass spectrometry interfaced by desorption electrospray ionization.

Science.gov (United States)

Lu, Mei; Wolff, Chloe; Cui, Weidong; Chen, Hao

2012-04-01

Recently we have shown that, as a versatile ionization technique, desorption electrospray ionization (DESI) can serve as a useful interface to combine electrochemistry (EC) with mass spectrometry (MS). In this study, the EC/DESI-MS method has been further applied to investigate some aqueous phase redox reactions of biological significance, including the reduction of peptide disulfide bonds and nitroaromatics as well as the oxidation of phenothiazines. It was found that knotted/enclosed disulfide bonds in the peptides apamin and endothelin could be electrochemically cleaved. Subsequent tandem MS analysis of the resulting reduced peptide ions using collision-induced dissociation (CID) and electron-capture dissociation (ECD) gave rise to extensive fragment ions, providing a fast protocol for sequencing peptides with complicated disulfide bond linkages. Flunitrazepam and clonazepam, a class of nitroaromatic drugs, are known to undergo reduction into amines which was proposed to involve nitroso and N-hydroxyl intermediates. Now in this study, these corresponding intermediate ions were successfully intercepted and their structures were confirmed by CID. This provides mass spectrometric evidence for the mechanism of the nitro to amine conversion process during nitroreduction, an important redox reaction involved in carcinogenesis. In addition, the well-known oxidation reaction of chlorpromazine was also examined. The putative transient one-electron transfer product, the chlorpromazine radical cation (m/z 318), was captured by MS, for the first time, and its structure was also verified by CID. In addition to these observations, some features of the DESI-interfaced electrochemical mass spectrometry were discussed, such as simple instrumentation and the lack of background signal. These results further demonstrate the feasibility of EC/DESI-MS for the study of the biology-relevant redox chemistry and would find applications in proteomics and drug development research.

One-step fabrication of PEGylated fluorescent nanodiamonds through the thiol-ene click reaction and their potential for biological imaging

Science.gov (United States)

Huang, Hongye; Liu, Meiying; Tuo, Xun; Chen, Junyu; Mao, Liucheng; Wen, Yuanqing; Tian, Jianwen; Zhou, Naigen; Zhang, Xiaoyong; Wei, Yen

2018-05-01

Over the past years, fluorescent carbon nanoparticles have got growing interest for biological imaging. Fluorescent nanodiamonds (FNDs) are novel fluorescent carbon nanoparticles with multitudinous useful properties, including remarkable fluorescence properties, extremely low toxicity and high refractive index. However, facile preparation of FNDs with designable properties and functions from non-fluorescent detonation nanodiamonds (DNDs) has demonstrated to be challengeable. In this work, we reported for the first time that preparation of Polyethylene glycol (PEG) functionalized FNDs through a one-step thiol-ene click reaction using thiol containing PEG (PEG-SH) as the coating agent. Based on the characterization results, we demonstrated that PEG-SH could be efficiently introduced on DNDs to obtain FNDs through the thiol-ene click chemistry. The resultant FND-PEG composites showed high water dispersibility, strong fluorescence and low cytotoxicity. Moreover, FND-PEG composites could be internalized by cells and displayed good cell dyeing performance. All of these features implied that FND-PEG composites are of great potential for biological imaging. Taken together, a facile one-step strategy based on the one-step thiol-ene click reaction has been developed for efficient preparation of FND-PEG composites from non-fluorescent DNDs. The strategy should be also useful for fabrication of many other functional FNDs via using different thiol containing compounds for the universality of thiol-ene click reaction.

Many-body treatment of subbarrier fusion reactions

Energy Technology Data Exchange (ETDEWEB)

Iwamoto, Akira; Kondratyev, V. [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Bonasera, A.

1998-07-01

The subbarrier fusion of heavy-ions at energies around the Coulomb barrier is studied by using semiclassical mean-field theory. The paths connecting entrance and exit subbarrier fusion reaction channels are found by incorporating the Wick transformation into the mean-field kinetic equation. The polarization and deformation of nuclei is shown to lower the barrier height. It is demonstrated that preequilibrium nucleon exchange in classically forbidden region gives rise to the nonlocal effects lowering the effective barrier further at small relative distance. (author)

VR-SCOSMO: A smooth conductor-like screening model with charge-dependent radii for modeling chemical reactions.

Science.gov (United States)

Kuechler, Erich R; Giese, Timothy J; York, Darrin M

2016-04-28

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational, produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.

Combustion chemical vapor desposited coatings for thermal barrier coating systems

Energy Technology Data Exchange (ETDEWEB)

Hampikian, J.M.; Carter, W.B. [Georgia Institute of Technology, Atlanta, GA (United States)

1995-10-01

The new deposition process, combustion chemical vapor deposition, shows a great deal of promise in the area of thermal barrier coating systems. This technique produces dense, adherent coatings, and does not require a reaction chamber. Coatings can therefore be applied in the open atmosphere. The process is potentially suitable for producing high quality CVD coatings for use as interlayers between the bond coat and thermal barrier coating, and/or as overlayers, on top of thermal barrier coatings.

Dose Response Model of Biological Reaction to Low Dose Rate Gamma Radiation

International Nuclear Information System (INIS)

Magae, J.; Furikawa, C.; Hoshi, Y.; Kawakami, Y.; Ogata, H.

2004-01-01

It is necessary to use reproducible and stable indicators to evaluate biological responses to long term irradiation at low dose-rate. They should be simple and quantitative enough to produce the results statistically accurate, because we have to analyze the subtle changes of biological responses around background level at low dose. For these purposes we chose micronucleus formation of U2OS, a human osteosarcoma cell line, as indicators of biological responses. Cells were exposed to gamma ray in irradiation rom bearing 50,000 Ci 60Co. After irradiation, they were cultured for 24 h in the presence of cytochalasin B to block cytokinesis, and cytoplasm and nucleus were stained with DAPI and prospidium iodide, respectively. the number of binuclear cells bearing micronuclei was counted under a fluorescence microscope. Dose rate in the irradiation room was measured with PLD. Dose response of PLD is linear between 1 mGy to 10 Gy, and standard deviation of triplicate count was several percent of mean value. We fitted statistically dose response curves to the data, and they were plotted on the coordinate of linearly scale response and dose. The results followed to the straight line passing through the origin of the coordinate axes between 0.1-5 Gy, and dose and does rate effectiveness factor (DDREF) was less than 2 when cells were irradiated for 1-10 min. Difference of the percent binuclear cells bearing micronucleus between irradiated cells and control cells was not statistically significant at the dose above 0.1 Gy when 5,000 binuclear cells were analyzed. In contrast, dose response curves never followed LNT, when cells were irradiated for 7 to 124 days. Difference of the percent binuclear cells bearing micronucleus between irradiated cells and control cells was not statistically significant at the dose below 6 Gy, when cells were continuously irradiated for 124 days. These results suggest that dose response curve of biological reaction is remarkably affected by exposure

Explore the reaction mechanism of the Maillard reaction: a density functional theory study.

Science.gov (United States)

Ren, Ge-Rui; Zhao, Li-Jiang; Sun, Qiang; Xie, Hu-Jun; Lei, Qun-Fang; Fang, Wen-Jun

2015-05-01

The mechanism of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution. The Maillard reaction is a cascade of consecutive and parallel reaction. In the present model system study, glucose and glycine were taken as the initial reactants. On the basis of previous experimental results, the mechanisms of Maillard reaction have been proposed, and the possibility for the formation of different compounds have been evaluated through calculating the relative energy changes for different steps of reaction under different pH conditions. Our calculations reveal that the TS3 in Amadori rearrangement reaction is the rate-determining step of Maillard reaction with the activation barriers of about 66.7 and 68.8 kcal mol(-1) in the gaseous phase and aqueous solution, respectively. The calculation results are in good agreement with previous studies and could provide insights into the reaction mechanism of Maillard reaction, since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.

Cold fusion in symmetric 90Zr induced reactions

International Nuclear Information System (INIS)

Keller, J.G.

1985-02-01

At the velocity filter SHIP of the Society for Heavy Ion Research in Darmstadt cross sections for evaporation-residue-nucleus formation in the reactions 90 Zr+ 89 Y, sup(90,92,96)Zr, 94 Mo were measured. In four of the reactions leading to the compound nuclei 179 Au, 180 Hg, 182 Hg, and 184 Pb for the first time in reactions of two heavy partners with mass numbers >20 radiative capture, i.e. deexcitation only by emission of γ radiation, was observed. A comparison of the measured cross sections for radiative capture with evaporation calculations leads to the final conclusion that either the γ-strength in the different compound nuclei is very different, or that the energy or angular momentum dependence of the level-density is wrongly described by the Fermi gas model at energies between 5 and 20 MeV. From the cross sections for evaporation-residue-nucleus formation fusion probabilities for central collisions were derived. The fusion probabilities show a strong dependence of the sub-barrier fusion from the nuclear structure of the contributing reaction partners. The slope of the fusion probability below the classical fusion barrier cannot be consistently described even by newer models. Below the lowest fusion barrier the fusion probability decreases with decreasing energy remarkably faster that predicted by a WKB calculation. This indicates that either the shape of the barrier is different from that predicted by the potentials, or that the mass dependence of the tunnel effect is not correctly described by the WKB calculation. (orig.) [de

Stochastic transport of particles across single barriers

International Nuclear Information System (INIS)

Kreuter, Christian; Siems, Ullrich; Henseler, Peter; Nielaba, Peter; Leiderer, Paul; Erbe, Artur

2012-01-01

Transport phenomena of interacting particles are of high interest for many applications in biology and mesoscopic systems. Here we present measurements on colloidal particles, which are confined in narrow channels on a substrate and interact with a barrier, which impedes the motion along the channel. The substrate of the particle is tilted in order for the particles to be driven towards the barrier and, if the energy gained by the tilt is large enough, surpass the barrier by thermal activation. We therefore study the influence of this barrier as well as the influence of particle interaction on the particle transport through such systems. All experiments are supported with Brownian dynamics simulations in order to complement the experiments with tests of a large range of parameter space which cannot be accessed in experiments.

Role of intestinal mucosal barrier in the development and progression of nonalcoholic fatty liver disease

Directory of Open Access Journals (Sweden)

ZHANG Yuanyuan

2016-12-01

Full Text Available The incidence of non-alcoholic fatty liver disease (NAFLD has been increasing year by year in China. Intestinal mucosa is the largest organ for bacterial storage, and intestinal mucosal barrier includes biological barrier, mechanical barrier, immunological barrier, and chemical barrier. This article investigates the important role of intestinal mucosal barrier function in the pathogenesis of NAFLD. As for the intestinal biological barrier, abnormalities in gut microbiota occur earlier than obesity and other metabolic disorders; small intestinal bacterial overgrowth may affect energy metabolism, promote insulin resistance, and get involved in the pathogenesis of NAFLD; regulation of gut microbiota has a certain clinical effect in the treatment of NAFLD. Intestinal mechanical barrier impairment increases the mucosal permeability and is associated with intestinal dysbacteriosis. The changes in intestinal immunological barrier may be associated with obesity, metabolic disorders, and liver inflammation. The changes in intestinal chemical barrier can inhibit the synthesis and secretion of very low-density lipoprotein and low-density lipoprotein in hepatocytes and may result in triglyceride deposition in the liver. It is pointed out that the research on intestinal mucosal barrier function provides promising prospects for the prevention and treatment of NAFLD.

Radiofrequency and extremely low-frequency electromagnetic field effects on the blood-brain barrier.

Science.gov (United States)

Nittby, Henrietta; Grafström, Gustav; Eberhardt, Jacob L; Malmgren, Lars; Brun, Arne; Persson, Bertil R R; Salford, Leif G

2008-01-01

During the last century, mankind has introduced electricity and during the very last decades, the microwaves of the modern communication society have spread a totally new entity--the radiofrequency fields--around the world. How does this affect biology on Earth? The mammalian brain is protected by the blood-brain barrier, which prevents harmful substances from reaching the brain tissue. There is evidence that exposure to electromagnetic fields at non thermal levels disrupts this barrier. In this review, the scientific findings in this field are presented. The result is a complex picture, where some studies show effects on the blood-brain barrier, whereas others do not. Possible mechanisms for the interactions between electromagnetic fields and the living organisms are discussed. Demonstrated effects on the blood-brain barrier, as well as a series of other effects upon biology, have caused societal anxiety. Continued research is needed to come to an understanding of how these possible effects can be neutralized, or at least reduced. Furthermore, it should be kept in mind that proven effects on biology also should have positive potentials, e.g., for medical use.

Investigations of nuclear structure and nuclear reactions induced by complex projectiles

International Nuclear Information System (INIS)

Sarantites, D.G.

1990-01-01

This report discusses research in the following areas: nuclear structure; fusion reactions near and below the barrier; incomplete fusion and fragmentation reactions; and instrumentation and analysis. (LSP)

Assessment of solid reactive mixtures for the development of biological permeable reactive barriers

International Nuclear Information System (INIS)

Pagnanelli, Francesca; Viggi, Carolina Cruz; Mainelli, Sara; Toro, Luigi

2009-01-01

Solid reactive mixtures were tested as filling material for the development of biological permeable reactive barriers for the treatment of heavy metals contaminated waters. Mixture selection was performed by taking into account the different mechanisms operating in sulphate and cadmium removal with particular attention to bioprecipitation and sorption onto the organic matrices in the mixtures. Suspensions of eight reactive mixtures were tested for sulphate removal (initial concentration 3 g L -1 ). Each mixture was made up of four main functional components: a mix of organic sources for bacterial growth, a neutralizing agent, a porous medium and zero-valent iron. The best mixture among the tested ones (M8: 6% leaves, 9% compost, 3% zero-valent iron, 30% silica sand, 30% perlite, 22% limestone) presented optimal conditions for SRB growth (pH 7.8 ± 0.1; E h = -410 ± 5 mV) and 83% sulphate removal in 22 days (25% due to bioreduction, 32% due to sorption onto compost and 20% onto leaves). M8 mixture allowed the complete abatement of cadmium with a significant contribution of sorption over bioprecipitation (6% Cd removal due to SRB activity). Sorption properties, characterised by potentiometric titrations and related modelling, were mainly due to carboxylic sites of organic components used in reactive mixtures.

Differentiation of closely related but biologically distinct cherry isolates of Prunus necrotic ringspot virus by polymerase chain reaction.

Science.gov (United States)

Hammond, R W; Crosslin, J M; Pasini, R; Howell, W E; Mink, G I

1999-07-01

Prunus necrotic ringspot ilarvirus (PNRSV) exists as a number of biologically distinct variants which differ in host specificity, serology, and pathology. Previous nucleotide sequence alignment and phylogenetic analysis of cloned reverse transcription-polymerase chain reaction (RT-PCR) products of several biologically distinct sweet cherry isolates revealed correlations between symptom type and the nucleotide and amino acid sequences of the 3a (putative movement protein) and 3b (coat protein) open reading frames. Based upon this analysis, RT-PCR assays have been developed that can identify isolates displaying different symptoms and serotypes. The incorporation of primers in a multiplex PCR protocol permits rapid detection and discrimination among the strains. The results of PCR amplification using type-specific primers that amplify a portion of the coat protein gene demonstrate that the primer-selection procedure developed for PNRSV constitutes a reliable method of viral strain discrimination in cherry for disease control and will also be useful for examining biological diversity within the PNRSV virus group.

Distribution and Biological Effects of Nanoparticles in the Reproductive System.

Science.gov (United States)

Liu, Ying; Li, Hongxia; Xiao, Kai

2016-01-01

Nanoparticles have shown great potential in biomedical applications such as imaging probes and drug delivery. However, the increasing use of nanoparticles has raised concerns about their adverse effects on human health and environment. Reproductive tissues and gametes represent highly delicate biological systems with the essential function of transmitting genetic information to the offspring, which is highly sensitive to environmental toxicants. This review aims to summarzie the penetration of physiological barriers (blood-testis barrier and placental barrier), distribution and biological effects of nanoparticles in the reproductive system, which is essential to control the beneficial effects of nanoparticles applications and to avoid their adverse effects on the reproductive system. We referred to a large number of relevant peer-reviewed research articles about the reproductive toxicity of nanoparticles. The comprehensive information was summarized into two parts: physiological barrier penetration and biological effects of nanoparticles in male or female reproductive system; distribution and metabolism of nanoparticles in the reproductive system. The representative examples were also presented in four tables. The in vitro and in vivo studies imply that some nanoparticles are able to cross the blood-testis barrier or placental barrier, and their penetration depends on the physicochemical characteristics of nanoparticles (e.g., composition, shape, particle size and surface coating). The toxicity assays indicate that nanoparticles might induce adverse physiological effects and impede fertility or embryogenesis. The barrier penetration, adverse physiological effects, distribution and metabolism are closely related to physicochemical characteristics of nanoparticles. Further systematic and mechanistic studies using well-characterized nanoparticles, relevant administration routes, and doses relevant to the expected exposure level are required to improve our

Application of the Trojan Horse Method to study neutron induced reactions: the 17O(n, α14C reaction

Directory of Open Access Journals (Sweden)

Gulino M.

2014-03-01

Full Text Available The reaction 17O(n, α14C was studied using virtual neutrons coming from the quasi-free deuteron break-up in the three body reaction 17O+d → α+14C+p. This technique, called virtual neutron method, extends the Trojan Horse method to neutron-induced reactions allowing to study the reaction cross section avoiding the suppression effects coming from the penetrability of the centrifugal barrier. For incident neutron energies from thermal up to a few hundred keV, direct experiments have shown the population of two out of three expected excited states at energies 8213 keV and 8282 keV and the influence of the sub-threshold level at 8038 keV. In the present experiment the 18O excited state at E* = 8.125 MeV, missing in the direct measurement, is observed. The angular distributions of the populated resonances have been measured for the first time. The results unambiguously indicate the ability of the method to overcome the centrifugal barrier suppression effect and to pick out the contribution of the bare nuclear interaction.

Measurements of barrier distributions for the system {sup 8}Li+{sup 120}Sn

Energy Technology Data Exchange (ETDEWEB)

Rossi Junior, E.S. [Centro Universitario FIEO (UNIFIEO), Osasco, SP (Brazil); Guimaraes, V.; Barioni, A.; Morais, M.C.; Faria, P.N. de; Lepine-Szily, A.; Lichtenthaeler Filho, R.; Crema, E.; Cardona, J.C.A. [Universidade de Sao Paulo (IF/USP), SP (Brazil). Inst. de Fisica; Monteiro, D.S. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Inst. de Fisica; Huiza, J.F.P. [Universidade Estadual do Sudoeste da Bahia (UESB), Jequie, BA (Brazil); Shorto, J.M.B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2011-07-01

Full text: The investigation of exotic nuclei, where the appearance of various effects and phenomena such as halo effect, skin of nucleons, new forms of decay, different spacing between the levels and new magic numbers in the shell model, has attracted a great motivation to investigate and study these nuclei in detail. Thus, important effects such as competition and interference between the reaction mechanisms, coupling between channels, can be investigated and analyzed in detail. The results of precise measurements of quasi-elastic barrier distributions can be used to develop and verify the validity of new models of reactions and new analytical techniques, making use of polarization potentials and calculations of CDCC (Continuum Discretized Coupled Channels). These measurements at energies near the Coulomb barrier can provide also information about the nuclear structure and reaction mechanisms. Recently, measurements of quasi-elastic barrier distributions for the system {sup 8}Li + {sup 120}Sn were carried out at energies around the Coulomb barrier (19.0, 20.4, 21.4 and 23.5 MeV) at the Pelletron laboratory. In this work, we will present the preliminary results of those measurements. (author)

Fusion reaction cross-sections using the Wong model within Skyrme energy density based semiclassical extended Thomas Fermi approach

Energy Technology Data Exchange (ETDEWEB)

Kumar, Raj, E-mail: rajkumarfzr@gmail.com [Department of Physics, Panjab University, Chandigarh-160014 (India); School of Physics and Material Science, Thapar University, Patiala-147004 (India); Sharma, Manoj K. [School of Physics and Material Science, Thapar University, Patiala-147004 (India); Gupta, Raj K. [Department of Physics, Panjab University, Chandigarh-160014 (India)

2011-11-15

First, the nuclear proximity potential, obtained by using the semiclassical extended Thomas Fermi (ETF) approach in Skyrme energy density formalism (SEDF), is shown to give more realistic barriers in frozen density approximation, as compared to the sudden approximation. Then, taking advantage of the fact that, in ETF method, different Skyrme forces give different barriers (height, position and curvature), we use the l-summed extended-Wong model of Gupta and collaborators (2009) under frozen densities approximation for calculating the cross-sections, where the Skyrme force is chosen with proper barrier characteristics, not-requiring additional 'barrier modification' effects (lowering or narrowing, etc.), for a best fit to data at sub-barrier energies. The method is applied to capture cross-section data from {sup 48}Ca + {sup 238}U, {sup 244}Pu, and {sup 248}Cm reactions and to fusion-evaporation cross-sections from {sup 58}Ni + {sup 58}Ni, {sup 64}Ni + {sup 64}Ni, and {sup 64}Ni + {sup 100}Mo reactions, with effects of deformations and orientations of nuclei included, wherever required. Interestingly, whereas the capture cross-sections in Ca-induced reactions could be fitted to any force, such as SIII, SV and GSkI, by allowing a small change of couple of units in deduced l{sub max}-values at below-barrier energies, the near-barrier data point of {sup 48}Ca + {sup 248}Cm reaction could not be fitted to l{sub max}-values deduced for below-barrier energies, calling for a check of data. On the other hand, the fusion-evaporation cross-sections in Ni-induced reactions at sub-barrier energies required different Skyrme forces, representing 'modifications of the barrier', for the best fit to data at all incident center-of-mass energies E{sub c.m.}'s, displaying a kind of fusion hindrance at sub-barrier energies. This barrier modification effect is taken into care here by using different Skyrme forces for reactions belonging to different regions of

Fusion barrier distributions - What have we learned?

International Nuclear Information System (INIS)

Hinde, D. J.; Dasgupta, M.

1998-01-01

The study of nuclear fusion received a strong impetus from the realisation that an experimental fusion barrier distribution could be determined from precisely measured fusion cross-sections. Experimental data for different reactions have shown in the fusion barrier distributions clear signatures of a range of nuclear excitations, for example the effects of static quadrupole and hexadecapole deformations, single- and double-phonon states, transfer of nucleons, and high-lying excited states. The improved understanding of fusion barrier distributions allows more reliable prediction of fusion angular momentum distributions, which aids interpretation of fission probabilities and fission anisotropies, and understanding of the population of super-deformed bands for nuclear structure studies. Studies of the relationship between the fusion barrier distribution and the extra-push energy should improve our understanding of the mechanism of the extra-push effect, and may help to predict new ways of forming very heavy or super-heavy nuclei

Study of Quasielastic scattering for 7Li+159Tb at around- barrier energies

Directory of Open Access Journals (Sweden)

Mukherjee A.

2017-01-01

Full Text Available Quasielastic scattering cross sections for the reaction 7Li+159Tb have been measured at large backangles, at energies around the Coulomb barrier. The quasielastic barrier distribution has been extracted from the measured quasielastic scattering excitation function, including and excluding α particle contribution. The peak of the quasielastic barrier distribution including α particle contribution shows a shift towards higher energy compared to the peak of the distribution without α particles. The quasielastic barrier distribution when compared to the calculated fusion barrier distribution, appears to show reasonable agreement for the system.

An annular ionization detector for quasi-elastic and transfer reaction studies

CERN Document Server

Dinesh, B V; Nayak, B K; Biswas, D C; Saxena, A; Pant, L M; Sahu, P K; Choudhury, R K

2000-01-01

An annular ionization chamber detector has been developed to study quasi-elastic and transfer reactions in heavy-ion collisions at near-barrier and sub-barrier energies. The important feature of the detector is that it has a near 2 pi coverage in the azimuthal angle phi for the particles entering in the detector at a given theta direction. This feature makes the detector very useful for measurement of the differential cross-sections at backward angles with respect to the beam direction, involving low cross-section reaction channels. The split anode configuration of the detector makes it capable of both particle identification and energy measurement for heavy ions and fission fragments. The detector has been tested using heavy-ion beams from the 14 MV-pelletron accelerator at Mumbai. Results on quasi-elastic excitation function measurements and barrier distribution studies in many heavy-ion reactions using this detector setup are discussed.

Decomposition mechanism of trichloroethylene based on by-product distribution in the hybrid barrier discharge plasma process

Energy Technology Data Exchange (ETDEWEB)

Han, Sang-Bo [Industry Applications Research Laboratory, Korea Electrotechnology Research Institute, Changwon, Kyeongnam (Korea, Republic of); Oda, Tetsuji [Department of Electrical Engineering, The University of Tokyo, Tokyo 113-8656 (Japan)

2007-05-15

The hybrid barrier discharge plasma process combined with ozone decomposition catalysts was studied experimentally for decomposing dilute trichloroethylene (TCE). Based on the fundamental experiment for catalytic activities on ozone decomposition, MnO{sub 2} was selected for application in the main experiments for its higher catalytic abilities than other metal oxides. A lower initial TCE concentration existed in the working gas; the larger ozone concentration was generated from the barrier discharge plasma treatment. Near complete decomposition of dichloro-acetylchloride (DCAC) into Cl{sub 2} and CO{sub x} was observed for an initial TCE concentration of less than 250 ppm. C=C {pi} bond cleavage in TCE gave a carbon single bond of DCAC through oxidation reaction during the barrier discharge plasma treatment. Those DCAC were easily broken in the subsequent catalytic reaction. While changing oxygen concentration in working gas, oxygen radicals in the plasma space strongly reacted with precursors of DCAC compared with those of trichloro-acetaldehyde. A chlorine radical chain reaction is considered as a plausible decomposition mechanism in the barrier discharge plasma treatment. The potential energy of oxygen radicals at the surface of the catalyst is considered as an important factor in causing reactive chemical reactions.

Dispersion relation approach to sub-barrier heavy ion fusion reactions

International Nuclear Information System (INIS)

Franzin, V.L.M.; Hussein, M.S.

1986-07-01

With the aid of an inverse dispersion relation, which gives the imaginary part of the fusion inclusive polarization potential (IPP) in terms of the principal part integral involving the real part of the IPP, the sub-barrier fusion of heavy ions is discussed. The system 16 O+ A Sm is taken as an example. The reactive content of the extracted IPP is analysed within the coupled channels theory. (Author) [pt

Barrier distribution in the heavy-ions fusion near Coulomb barrier

International Nuclear Information System (INIS)

Shilov, V.M.

1992-01-01

Experimental data on fusion cross section and average angular momenta of the compound nucleus are analyzed on the basis of the coupled-channel model for the reactions 32 S+ 100 Mo and 36 S+ 96 Mo. It is shown that it is important to take into account the transfer channels with positive value Q r for the description of the data. The intermediate coupling between excited states changes the distribution of barriers and approximates them to the ones of the Stelson phenomenological model. 22 refs.; 4 figs.; 2 tabs

Near-Surface Engineered Environmental Barrier Integrity

International Nuclear Information System (INIS)

Piet, S.J.; Breckenridge, R.P.

2002-01-01

The INEEL Environmental Systems Research and Analysis (ESRA) program has launched a new R and D project on Near-Surface Engineered Environmental Barrier Integrity to increase knowledge and capabilities for using engineering and ecological components to improve the integrity of near-surface barriers used to confine contaminants from the public and the environment. The knowledge gained and the capabilities built will help verify the adequacy of past remedial decisions and enable improved solutions for future cleanup decisions. The research is planned to (a) improve the knowledge of degradation mechanisms (weathering, biological, geological, chemical, radiological, and catastrophic) in times shorter than service life, (b) improve modeling of barrier degradation dynamics, (c) develop sensor systems to identify degradation prior to failure, and (d) provide a better basis for developing and testing of new barrier systems to increase reliability and reduce the risk of failure. Our project combine s selected exploratory studies (benchtop and field scale), coupled effects accelerated aging testing and the meso-scale, testing of new monitoring concepts, and modeling of dynamic systems. The performance of evapo-transpiration, capillary, and grout-based barriers will be examined

Quantum Mechanics/Molecular Mechanics Free Energy Maps and Nonadiabatic Simulations for a Photochemical Reaction in DNA: Cyclobutane Thymine Dimer.

Science.gov (United States)

Mendieta-Moreno, Jesús I; Trabada, Daniel G; Mendieta, Jesús; Lewis, James P; Gómez-Puertas, Paulino; Ortega, José

2016-11-03

The absorption of ultraviolet radiation by DNA may result in harmful genetic lesions that affect DNA replication and transcription, ultimately causing mutations, cancer, and/or cell death. We analyze the most abundant photochemical reaction in DNA, the cyclobutane thymine dimer, using hybrid quantum mechanics/molecular mechanics (QM/MM) techniques and QM/MM nonadiabatic molecular dynamics. We find that, due to its double helix structure, DNA presents a free energy barrier between nonreactive and reactive conformations leading to the photolesion. Moreover, our nonadiabatic simulations show that most of the photoexcited reactive conformations return to standard B-DNA conformations after an ultrafast nonradiative decay to the ground state. This work highlights the importance of dynamical effects (free energy, excited-state dynamics) for the study of photochemical reactions in biological systems.

Mapping the kinetic barriers of a Large RNA molecule's folding landscape.

Directory of Open Access Journals (Sweden)

Jörg C Schlatterer

Full Text Available The folding of linear polymers into discrete three-dimensional structures is often required for biological function. The formation of long-lived intermediates is a hallmark of the folding of large RNA molecules due to the ruggedness of their energy landscapes. The precise thermodynamic nature of the barriers (whether enthalpic or entropic that leads to intermediate formation is still poorly characterized in large structured RNA molecules. A classic approach to analyzing kinetic barriers are temperature dependent studies analyzed with Eyring's transition state theory. We applied Eyring's theory to time-resolved hydroxyl radical (•OH footprinting kinetics progress curves collected at eight temperature from 21.5 °C to 51 °C to characterize the thermodynamic nature of folding intermediate formation for the Mg(2+-mediated folding of the Tetrahymena thermophila group I ribozyme. A common kinetic model configuration describes this RNA folding reaction over the entire temperature range studied consisting of primary (fast transitions to misfolded intermediates followed by much slower secondary transitions, consistent with previous studies. Eyring analysis reveals that the primary transitions are moderate in magnitude and primarily enthalpic in nature. In contrast, the secondary transitions are daunting in magnitude and entropic in nature. The entropic character of the secondary transitions is consistent with structural rearrangement of the intermediate species to the final folded form. This segregation of kinetic control reveals distinctly different molecular mechanisms during the two stages of RNA folding and documents the importance of entropic barriers to defining rugged RNA folding landscapes.

High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction

Science.gov (United States)

Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.; Schaefer, Henry F.

2018-05-01

Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol-1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol-1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radical (QOOH) that eventually decomposes to formaldehyde, CO, and •OH. Two other unimolecular reactions of the peroxy radical are α-hydrogen abstraction (38.7 kcal mol-1 barrier) and HO2• elimination (43.5 kcal mol-1 barrier). These pathways lead to glyoxal + •OH and ketene + HO2• formation, respectively, but they are expected to be uncompetitive due to their high barriers.

Three key points along an intrinsic reaction coordinate

Indian Academy of Sciences (India)

Unknown

Abstract. The concept of the reaction force is presented and discussed in detail. For typical processes with energy barriers, it has a universal form which defines three key points along an intrinsic reaction co- ordinate: the force minimum, zero and maximum. We suggest that the resulting four zones be interpreted as involving ...

EVALUATION OF AMENDMENTS FOR MENDING THE INSITU REDOX MANIPULATION (ISRM) BARRIER

Energy Technology Data Exchange (ETDEWEB)

PETERSEN, S.W.

2006-02-07

In May of 2004, the U.S. Department of Energy (DOE) Richland and Fluor Hanford requested technical assistance from DOE Headquarters EM-23 to provide a team of technical experts to evaluate likely chemical/biological amendments for mending the In Situ Redox Manipulation (ISRM) Barrier in the 100-D Area of the Hanford Site. This request was a follow-on to an earlier request for assistance regarding the cause of chromium (Cr) breakthrough and recommendations for mending the barrier (March 2004 workshop). This report provides written documentation of the team's findings and recommendations. In 1995, a plume of dissolved hexavalent chromium [Cr(VI)] was discovered along the Columbia River shoreline and in the 100-D Area. Between 1999 and 2003, a reactive barrier using the ISRM technology, was installed at a distance of 680 meters along the river to reduce the Cr(VI) in the groundwater. The ISRM technology creates a treatment zone within the aquifer by injection of sodium dithionite, a strong reducing agent that scavenges dissolved oxygen (DO) from the aquifer and reduces ferric iron [Fe(III)], related metals, and oxy-ions. Bench-scale and field-scale treatability tests were conducted to demonstrate proof-of principle and to estimate barrier longevity, calculated to be in excess of twenty years. However, several years after initial and secondary treatment, groundwater in approximately 17 wells has been found to contain elevated Cr concentrations. The March 2004 technical assistance team (TAT) identified potential causes of Cr breakthrough as likely related to physical and chemical heterogeneity within the aquifer (including loss of reductive capacity within preferential flow paths) and the presence of other oxidants (DO and nitrate) significantly affecting the reductive capacity of the treated aquifer. These aquifer characteristics may limit the ability of alternative amendments to extend the reducing capacity of the barrier. A 2001 Bechtel Hanford report and

Recent results on fusion and direct reactions with weakly bound stable nuclei

International Nuclear Information System (INIS)

Shrivastava, A.

2011-01-01

Recent measurements of fusion and direct reactions in case of weakly bound stable nuclei at extreme sub-barrier energies using a sensitive off beam technique are presented. First section deals with deep sub-barrier fusion cross-section measurement for 67 Li + 198 Pt followed by the study of fragment capture reaction of 7 Li + 198 Pt. Deviation in the slope of the fusion excitation function, as observed in case of medium heavy systems, is absent in the present asymmetric systems at these low energies. This study shows the absence of fusion hindrance, suggesting modifications in models that explain deep sub-barrier fusion data to incorporate weakly bound asymmetric systems

Exploring dissipative processes at high angular momentum in 58Ni+60Ni reactions

Directory of Open Access Journals (Sweden)

Williams E.

2016-01-01

Full Text Available Current coupled channels (CC models treat fusion as a coherent quantum-mechanical process, in which coupling between the collective states of the colliding nuclei influences the probability of fusion in near-barrier reactions. While CC models have been used to successfully describe many experimental fusion barrier distribution (BD measurements, the CC approach has failed in the notable case of 16O+208Pb. The reason for this is poorly understood; however, it has been postulated that dissipative processes may play a role. Traditional BD experiments can only probe the physics of fusion for collisions at the top of the Coulomb barrier (L = 0ħ. In this work, we will present results using a novel method of probing dissipative processes inside the Coulomb barrier. The method exploits the predicted sharp onset of fission at L ~ 60ħ for reactions forming compound nuclei with A < 160. Using the ANU’s 14UD tandem accelerator and CUBE spectrometer, reaction outcomes have been measured for the 58Ni+60Ni reaction at a range of energies, in order to explore dissipative processes at high angular momentum. In this reaction, deep inelastic processes have been found to set in before the onset fission at high angular momentum following fusion. The results will be discussed in relation to the need for a dynamical model of fusion.

Paradigms for biologically inspired design

DEFF Research Database (Denmark)

Lenau, T. A.; Metzea, A.-L.; Hesselberg, T.

2018-01-01

engineering, medical engineering, nanotechnology, photonics,environmental protection and agriculture. However, a major obstacle for the wider use of biologically inspired design isthe knowledge barrier that exist between the application engineers that have insight into how to design suitable productsand......Biologically inspired design is attracting increasing interest since it offers access to a huge biological repository of wellproven design principles that can be used for developing new and innovative products. Biological phenomena can inspireproduct innovation in as diverse areas as mechanical...... the biologists with detailed knowledge and experience in understanding how biological organisms function in theirenvironment. The biologically inspired design process can therefore be approached using different design paradigmsdepending on the dominant opportunities, challenges and knowledge characteristics...

Analysis of kinetic reaction mechanisms

CERN Document Server

Turányi, Tamás

2014-01-01

Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

Standards for the Protection of Skin Barrier Function.

Science.gov (United States)

Giménez-Arnau, Ana

2016-01-01

The skin is a vital organ, and through our skin we are in close contact with the entire environment. If we lose our skin we lose our life. The barrier function of the skin is mainly driven by the sophisticated epidermis in close relationship with the dermis. The epidermal epithelium is a mechanically, chemically, biologically and immunologically active barrier submitted to continuous turnover. The barrier function of the skin needs to be protected and restored. Its own physiology allows its recovery, but many times this is not sufficient. This chapter is focused on the standards to restore, treat and prevent barrier function disruption. These standards were developed from a scientific, academic and clinical point of view. There is a lack of standardized administrative recommendations. Still, there is a walk to do that will help to reduce the social and economic burden of diseases characterized by an abnormal skin barrier function. © 2016 S. Karger AG, Basel.

The "1"2C("1"6O,γ"2"8Si) radiative capture reaction at sub-barrier energies

International Nuclear Information System (INIS)

Goasduff, A.; Courtin, S.; Haas, F.; Lebhertz, D.; Jenkins, D.G.; Fallis, J.; Ruiz, C.; Hutcheon, D.A.; Amandruz, P.A.; Davis, C.; Hager, U.; Ottewell, D.; Ruprecht, G.

2014-01-01

The heavy-ion radiative capture "1"2C("1"6O,γ"2"8Si) was measured at the sub-Coulomb barrier bombarding energy E(lab) = 15.7 MeV, which corresponds to the lowest important resonance observed in the "1"2C + "1"6O fusion excitation function. Thanks to combination of the bismuth germanate (BGO) γ-ray array and the 0 degree DRAGON electromagnetic spectrometer at TRIUMF, the γ-decay spectrum from the entrance channel down to the ground state of "2"8Si was measured. Comparisons of the experimental spectrum to γ spectrum extracted from Monte-Carlo simulations of the complete setup suggest a J"π = 2"+ spin-parity assignment to the entrance channel and yield the radiative capture cross section σ(RC) = 0.22 ± 0.04 μb. Combining this present spin assignment with previous data on radiative capture, a J (J + 1) systematics was constructed, and it indicated a moment of inertia commensurate with the "1"2C+"1"6O grazing angular momentum. Strong dipole transitions are observed from the entrance channel to T = 1 states around 11.5 MeV and are found to result from enhanced M1_I_V transitions to states exhausting a large part of the M1 sum rule built on the ground state of "2"8Si. This specific decay was also reported at bombarding energies close to the Coulomb barrier in our previous study of the "1"2C("1"2C,γ"2"4Mg) heavy-ion radiative capture reaction. Similarities between both systems are investigated. (authors)

Bimolecular reactions of carbenes: Proton transfer mechanism

Science.gov (United States)

Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

2018-04-01

Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

The rate of the reaction between CN and C2H2 at interstellar temperatures

Science.gov (United States)

Woon, D. E.; Herbst, E.

1997-01-01

The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

Potential and barriers for biogas production in Denmark at widely expanded organic farming with focus on the soil carbon content; Potentiale og barrierer for biogasproduktion i Danmark ved omfattende oekologisk jordbrug med fokus paa dyrkningsjordens kulstofforhold

Energy Technology Data Exchange (ETDEWEB)

Buch Salomonsen, K.

2000-06-01

The Ph.D. thesis describes the influence from continued expansion of organic farming systems to the potential for energy production from biogas in Denmark. The project analyses the consequence from three categories of barriers: 1) Practical barriers, 2) The attitude of organic farmers, and 3) Agricultural biological problems. Economic and political barriers are not examined. When the barriers can be quantified, they are included in the calculation of the maximum biogas potential. When not, the implications of barriers are expressed qualitatively. It has been a particular goal to provide new information on whether agricultural biological problems are a barrier to biogas production in organic farming systems. One important question in this connection is whether biogas production has a negative influence on the soil carbon content compared to composting. This question is investigated by an experiment. The project is based on technical and natural science disciplines, with an interdisciplinary basis ranging over energy planning, agricultural science, microbiology, and crop, and animal operation. (au)

Micro/nanofabricated environments for synthetic biology.

Science.gov (United States)

Collier, C Patrick; Simpson, Michael L

2011-08-01

A better understanding of how confinement, crowding and reduced dimensionality modulate reactivity and reaction dynamics will aid in the rational and systematic discovery of functionality in complex biological systems. Artificial microfabricated and nanofabricated structures have helped elucidate the effects of nanoscale spatial confinement and segregation on biological behavior, particularly when integrated with microfluidics, through precise control in both space and time of diffusible signals and binding interactions. Examples of nanostructured interfaces for synthetic biology include the development of cell-like compartments for encapsulating biochemical reactions, nanostructured environments for fundamental studies of diffusion, molecular transport and biochemical reaction kinetics, and regulation of biomolecular interactions as functions of microfabricated and nanofabricated topological constraints. Copyright © 2011 Elsevier Ltd. All rights reserved.

Fusion and quasi-elastic processes near the Coulomb barrier

International Nuclear Information System (INIS)

Abriola, D.

1987-01-01

An overview of the fusion phenomenon below Coulomb barrier is presented. The current theoretical descriptions, emphasizing the relations with direct reactions are discussed. The definition and systematic behaviour of the fusion enhancement below the Coulomb barrier are also presented. The role of coupling to surface degrees of freedom, namely permanent deformations of nuclei, inelastic and transfer channels is shown. The importance of studies describing simultaneously quase-elastic processes and fusion are also shown. (M.C.K.) [pt

8B + 208Pb Elastic Scattering at Coulomb Barrier Energies

Science.gov (United States)

La Commara, M.; Mazzocco, M.; Boiano, A.; Boiano, C.; Manea, C.; Parascandolo, C.; Pierroutsakou, D.; Signorini, C.; Strano, E.; Torresi, D.; Yamaguchi, H.; Kahl, D.; Di Meo, P.; Grebosz, J.; Imai, N.; Hirayama, Y.; Ishiyama, H.; Iwasa, N.; Jeong, S. C.; Jia, H. M.; Kim, Y. H.; Kimura, S.; Kubono, S.; Lin, C. J.; Miyatake, H.; Mukai, M.; Nakao, T.; Nicoletto, M.; Sakaguchi, Y.; Sánchez-Benítez, A. M.; Soramel, F.; Teranishi, T.; Wakabayashi, Y.; Watanabe, Y. X.; Yang, L.; Yang, Y. Y.

2018-02-01

The scattering process of weakly-bound nuclei at Coulomb barrier energies provides deep insights on the reaction dynamics induced by exotic nuclei. Within this framework, we measured for the first time the scattering process of the short-lived Radioactive Ion Beam (RIB) 8B (Sp = 0.1375 MeV) from a 208Pb target at 50 MeV beam energy. The 8B RIB was produced by means of the in-flight facility CRIB (RIKEN, Japan) with an average intensity on target of 10 kHz and a purity about 25%. Elastically scattering ions were detected in the angular range θc.m. = 10°-160° by means of the detector array EXPADES. A preliminary optical model analysis indicates a total reaction cross section of about 1 b, a value, once reduced, 2-3 times larger than those obtained for the reactions induced by the stable weakly-bound projectiles 6,7Li on a 208Pb target in the energy range around the Coulomb barrier.

MOLNs: A CLOUD PLATFORM FOR INTERACTIVE, REPRODUCIBLE, AND SCALABLE SPATIAL STOCHASTIC COMPUTATIONAL EXPERIMENTS IN SYSTEMS BIOLOGY USING PyURDME.

Science.gov (United States)

Drawert, Brian; Trogdon, Michael; Toor, Salman; Petzold, Linda; Hellander, Andreas

2016-01-01

Computational experiments using spatial stochastic simulations have led to important new biological insights, but they require specialized tools and a complex software stack, as well as large and scalable compute and data analysis resources due to the large computational cost associated with Monte Carlo computational workflows. The complexity of setting up and managing a large-scale distributed computation environment to support productive and reproducible modeling can be prohibitive for practitioners in systems biology. This results in a barrier to the adoption of spatial stochastic simulation tools, effectively limiting the type of biological questions addressed by quantitative modeling. In this paper, we present PyURDME, a new, user-friendly spatial modeling and simulation package, and MOLNs, a cloud computing appliance for distributed simulation of stochastic reaction-diffusion models. MOLNs is based on IPython and provides an interactive programming platform for development of sharable and reproducible distributed parallel computational experiments.

Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin

Science.gov (United States)

Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo

2016-02-01

Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

Reaction rate calculations via transmission coefficients

International Nuclear Information System (INIS)

Feit, M.D.; Alder, B.J.

1985-01-01

The transmission coefficient of a wavepacket traversing a potential barrier can be determined by steady state calculations carried out in imaginary time instead of by real time dynamical calculations. The general argument is verified for the Eckart barrier potential by a comparison of transmission coefficients calculated from real and imaginary time solutions of the Schroedinger equation. The correspondence demonstrated here allows a formulation for the reaction rate that avoids difficulties due to both rare events and explicitly time dependent calculations. 5 refs., 2 figs

Biological and Sociocultural Differences in Perceived Barriers to Physical Activity Among Fifth- to Seventh-Grade Urban Girls.

Science.gov (United States)

Vermeesch, Amber L; Ling, Jiying; Voskuil, Vicki R; Bakhoya, Marion; Wesolek, Stacey M; Bourne, Kelly A; Pfeiffer, Karin A; Robbins, Lorraine B

2015-01-01

Inadequate physical activity (PA) contributes to the high prevalence of overweight and obesity among U.S. adolescent girls. Barriers preventing adolescent girls from meeting PA guidelines have not been thoroughly examined. The threefold purpose of this study was to (a) determine pubertal stage, racial/ethnic, and socioeconomic status (SES) differences in ratings of interference of barriers to PA; (b) examine relationships between perceived barriers and age, body mass index, recreational screen time, sedentary activity, and PA; and (c) identify girls' top-rated perceived barriers to PA. Girls (N = 509) from eight Midwestern U.S. schools participated. Demographic, pubertal stage, perceived barriers, and recreational screen time data were collected via surveys. Height and weight were measured. Accelerometers measured sedentary activity, moderate-to-vigorous PA (MVPA), and light plus MVPA. Girls of low SES reported greater interference of perceived barriers to PA than those who were not of low SES (1.16 vs. 0.97, p = .01). Girls in early/middle puberty had lower perceived barriers than those in late puberty (1.03 vs. 1.24, p barriers were negatively related to MVPA (r = -.10, p = .03) and light plus MVPA (r = -.11, p = .02). Girls' top five perceived barriers included lack of skills, hating to sweat, difficulty finding programs, being tired, and having pain. Innovative interventions, particularly focusing on skill development, are needed to assist girls in overcoming their perceived barriers to PA.

Gamma rays as probe of fission and quasi-fission dynamics in the reaction 32S + 197Au near the Coulomb barrier

Science.gov (United States)

Pulcini, A.; Vardaci, E.; Kozulin, E.; Ashaduzzaman, M.; Borcea, C.; Bracco, A.; Brambilla, S.; Calinescu, S.; Camera, F.; Ciemala, M.; de Canditiis, B.; Dorvaux, O.; Harca, I. M.; Itkis, I.; Kirakosyan, V. V.; Knyazheva, G.; Kozulina, N.; Kolesov, I. V.; La Rana, G.; Maj, A.; Matea, I.; Novikov, K.; Petrone, C.; Quero, D.; Rath, P.; Saveleva, E.; Schmitt, C.; Sposito, G.; Stezowski, O.; Trzaska, W. H.; Wilson, J.

2018-05-01

Compound nucleus fission and quasi-fission are both binary decay channels whose common properties make the experimental separation between them difficult. A way to achieve this separation could be to probe the angular momentum of the binary fragments. This can be done detecting gamma rays in coincidence with the two fragments. As a case study, the reaction 32S + 197Au near the Coulomb barrier has been performed at the Tandem ALTO facility at IPN ORSAY. ORGAM and PARIS, two different gamma detectors arrays, are coupled with the CORSET detector, a two-arm time-of-flight spectrometer. TOF-TOF data were analyzed to reconstruct the mass-energy distribution of the primary fragments coupled with gamma multiplicity and spectroscopic analysis. Preliminary results of will be shown.

Reaction cross sections and elastic scattering energy dependence around the Coulomb barrier for the {sup 7}Be+{sup 27}Al system

Energy Technology Data Exchange (ETDEWEB)

Morcelle, Viviane; Gomes, P.R.S.; Lubian, J.; Mendes Junior, D.R. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil); Lichtenthaeler, R.; Guimaraes, V.; Lepine-Szily, A.; Camargo, O.; Faria, P.N. de; Gasquez, L.; Morais, M.C.; Condori, R.P.; Pires, K.C.C.; Scarduelli, V. [Universidade de Sao Paulo (USP), SP (Brazil); Barioni, A. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil); Shorto, J.M.B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Zamora, J.C. [Technische Universitaet Darmstadt (Germany); Aguilera, E.; Martinez-Quiroz, E. [Instituto Nacional de Investigaciones Nucleares (Mexico); Kolata, J.; Jiang, H. [University of Notre Dame, IN (United States); Bechetti, F.D.; Lamm, L.O. [Michigan University, MI (United States); Lizcano, D. [Universidad Autonoma del Estado de Mexico (Mexico)

2012-07-01

Full text: Elastic scattering measurements were performed at energies around the Coulomb barrier at the Tandem Accelerators of the Sao Paulo (USP - Brazil ) and Notre Dame (UND - USA) Universities. The {sup 7}Be is a radioactive nucleus and has been produced by the reaction {sup 6}He({sup 6}Li,{sup 9}Be) and impinged on {sup 27}Al and {sup 197}Au secondary targets using a double superconducting systems RIBRAS ( USP ) and Twinsol (UND). The elastic scattering angular distributions were analyzed through the optical model calculations, using the Woods- Saxon form factors [1] and the Sao Paulo potential [2] to fit the experimental data. The total reaction cross sections were also derived and compared with others presented at the literature for other systems. In addition, a study of the nuclear potential energy dependence has been carried out in this work in the dispersion relation context. Due to the fact that {sup 7}Be has a small breakup threshold energy, the results can provide significant information of the influence of the breakup channel on the reactions involving this projectile. For this purpose, {chi}{sup 2}- data analysis with different kind of potentials were performed to identify the energy dependence of the real (V) and imaginary (W) parts of the potential. [1] L.C. Chamon et al., Phys. Rev. C 66, (2002) 014610. [2] R.D. Wood e D.S. Saxon, Phys. Rev. 95 ( 1954) 577. (author)

Alpha-induced instabilities in tandem thermal barriers

Energy Technology Data Exchange (ETDEWEB)

Kammash, T.; Galbraith, D.L.

1987-01-01

A major premise in the operation of Tandem Mirror reactors is that the fusion reactions take place in the central cell only. The alpha particles generated by the Deuterium-Tritium (DT) fusions, along with other ions, will however pass from the central cell to the thermal barriers and return to the central cell as a result of reflection by the potential hills that exist by the plugs' side of these barriers. This streaming motion gives rise to electrostatic and electomagnetic instabilities which could detract from the barrier's function as a thermal insulator. The number density and streaming velocity of these passing particles are dictated by the electrostatic potential variation and the magnetic field structure in these regions. It is shown that, in the absence of alphas, barriers with deep potential depression are less susceptible to electrostatic instabilities while particularly vulnerable to unstable electromagnetic modes. In the presence of alphas, especially the fast alphas whose mean energy is significantly larger than the barrier potentials they see, (which is twice as high as that seen by the ions) both types of modes become unstable.

Near and sub-barrier fusion studies with radioactive nuclei: an overview

International Nuclear Information System (INIS)

Majumdar, Harashit

2004-01-01

Full text: Understanding of the reaction mechanism with radioactive nuclei, e.g., halo nuclei, at near barrier energies appears to be a challenging problem at present. Recent experimental and theoretical investigations of fusion of exotic nuclei with stable targets have yielded new insights into the structure of these nuclei and its effects on the fusion reaction dynamics. One interesting and intriguing result of this type of study is the controversy over fusion enhancement in the presence of strong break-up channels. Other novel information include an increase of break-up cross-sections and weakening or absence of threshold anomaly, related to energy dependence of optical model potentials, in the neighbourhood of the barrier. It is believed that the coupling of the entrance channel to different non-elastic channels (including break-up) is responsible for the above phenomena and these aspects are more prominent in the near barrier region. An overview of the experimental studies of fusion excitation function with RIB will be presented

Near and sub-barrier fusion studies with radioactive nuclei: an overview

International Nuclear Information System (INIS)

Majumdar, Harashit

2004-01-01

Full Text: Understanding of the reaction mechanism with radioactive nuclei, e.g., halo nuclei, at near barrier energies appears to be a challenging problem at present. Recent experimental and theoretical investigations of fusion of exotic nuclei with stable targets have yielded new insights into the structure of these nuclei and its effects on the fusion reaction dynamics. One interesting and intriguing result of this type of study is the controversy over fusion enhancement in the presence of strong break-up channels. Other novel information include an increase of break-up cross-sections and weakening or absence of threshold anomaly, related to energy dependence of optical model potentials, in the neighbourhood of the barrier. It is believed that the coupling of the entrance channel to different non-elastic channels (including break-up) is responsible for the above phenomena and these aspects are more prominent in the near barrier region. An overview of the experimental studies of fusion excitation function with RIB will be presented

Apparent tunneling in chemical reactions

DEFF Research Database (Denmark)

Henriksen, Niels Engholm; Hansen, Flemming Yssing; Billing, G. D.

2000-01-01

A necessary condition for tunneling in a chemical reaction is that the probability of crossing a barrier is non-zero, when the energy of the reactants is below the potential energy of the barrier. Due to the non-classical nature (i.e, momentum uncertainty) of vibrational states this is, however......, not a sufficient condition in order to establish genuine tunneling as a result of quantum dynamics. This proposition is illustrated for a two-dimensional model potential describing dissociative sticking of N-2 on Ru(s). It is suggested that the remarkable heavy atom tunneling, found in this system, is related...

Performance of engineered barriers for low-level waste

International Nuclear Information System (INIS)

Taplin, D.; Claridge, F.B.

1987-09-01

Geotechnical Resources Ltd., in association with Komex Consultants Ltd., was retained to collect, synthesize and evaluate the available information on the long term performance of engineered barriers for low-level radioactive wastes disposed in Canada. Literature was researched from Canadian, United States and European sources. A variety of barrier materials were assessed in the study and included natural clays, concrete and cement, metals, bentonite-sand admixes, bitumen and bituminous admixes, soil cement and polymeric membranes. The generalized geological and geotechnical conditions encountered within the soil and rock host media currently under consideration for disposal sites in southern Ontario were also summarized. Both internal barriers, or buffers, to immobilize the waste material and reduce radionuclide mobility, as well as external barriers to limit the migration of contaminants were examined. Microbial activities within the waste forms were analyzed, including cellulose degradation, methanogenesis and bicarbonate and organic reactions. Microbial interactions with the various engineered barrier materials under consideration were also assessed. Finally, the anticipated long term performances of the respective barrier materials under consideration were evaluated, along with the general suitability of the geological host media being proposed for disposal sites

Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model

NARCIS (Netherlands)

Bickelhaupt, F. Matthias; Houk, Kendall N.

2017-01-01

The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction

Low energy ion-molecule reactions

International Nuclear Information System (INIS)

Farrar, J.M.

1986-01-01

The authors work during the past year has focused on several problems in the condensation reactions of C + and CH 3 + with small molecules, particularly hydrocarbons. Their emphasis has been on understanding the dynamics of collision complex formation and isomerization of transient intermediates along the reaction coordinate. In many ionic reactions, intermediates having non-classical valence structures may be nearly as stable as their classical analogs, in contrast with neutral systems where the non-classical structures are much less stable. The C + + NH 3 system shows this behavior, indicating that the non-classical HCNH 2 + structure formed by insertion of C + into the N-H bond serves as a precursor to the products. N-H bond cleavage in this intermediate to form HCNH + occurs over a large barrier and occurs more readily than the 1,2 hydrogen atom shift to form the classical H 2 C = NH + intermediate. Their experimental kinetic energy distribution for this channel is consistent with the presence of a large exit channel barrier. Their recently published work on C + + H 2 O also demonstrates this phenomenon. The CHOH + hydroxycarbene cation serves as the initial intermediate and isomerization to the classical H 2 CO + cation is competitive with O-H or C-H cleavage to yield the formyl, HCO + , or isoformyl, COH + , cations. They have also completed studies on the reactions of C + with O 2 , CH 3 OH, HCN, and the two-carbon containing hydrocarbons ethane, ethylene, and acetylene

Heavy ion collisions at energies near the Coulomb barrier 1990

International Nuclear Information System (INIS)

Nagarajan, M.A.

1991-01-01

During recent years, detailed experimental and theoretical investigations have been carried out on heavy ion collisions at energies close to the Coulomb barrier. These studies have provided direct evidence of strong couplings between the various reaction channels available at energies near the top of the Coulomb barrier. This field of research has remained the focus of interest and with improved experimental techniques, new detailed high resolution data have been obtained. The workshop on ''Heavy Ion Collisions at Energies Close to the Coulomb Barrier'' was organized with the aim of reviewing the current understanding of the collision dynamics and to discuss future directions in this area of research. The topics discussed at the workshop were broadly classified under the titles: quasielastic reactions; fusion of heavy ions; and shape and spin dependence in heavy ion collisions. The last of these topics was included to review new data obtained with polarized heavy ions and their theoretical interpretations. This volume contains the invited and contributed talks as well as a few short presentations during panel discussions. (author)

Development of Bioorthogonal Reactions and Their Applications in Bioconjugation

Directory of Open Access Journals (Sweden)

Mengmeng Zheng

2015-02-01

Full Text Available Biomolecule labeling using chemical probes with specific biological activities has played important roles for the elucidation of complicated biological processes. Selective bioconjugation strategies are highly-demanded in the construction of various small-molecule probes to explore complex biological systems. Bioorthogonal reactions that undergo fast and selective ligation under bio-compatible conditions have found diverse applications in the development of new bioconjugation strategies. The development of new bioorthogonal reactions in the past decade has been summarized with comments on their potentials as bioconjugation method in the construction of various biological probes for investigating their target biomolecules. For the applications of bioorthogonal reactions in the site-selective biomolecule conjugation, examples have been presented on the bioconjugation of protein, glycan, nucleic acids and lipids.

Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

International Nuclear Information System (INIS)

Bartling, Stephan; Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

2015-01-01

Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology

Vision 2020. Reaction Engineering Roadmap

Energy Technology Data Exchange (ETDEWEB)

Klipstein, David H. [Reaction Design, San Diego, CA (United States); Robinson, Sharon [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2001-01-01

The Reaction Engineering Roadmap is a part of an industry- wide effort to create a blueprint of the research and technology milestones that are necessary to achieve longterm industry goals. This report documents the results of a workshop focused on the research needs, technology barriers, and priorities of the chemical industry as they relate to reaction engineering viewed first by industrial use (basic chemicals; specialty chemicals; pharmaceuticals; and polymers) and then by technology segment (reactor system selection, design, and scale-up; chemical mechanism development and property estimation; dealing with catalysis; and new, nonstandard reactor types).

Degradations and Rearrangement Reactions

Science.gov (United States)

Zhang, Jianbo

This section deals with recent reports concerning degradation and rearrangement reactions of free sugars as well as some glycosides. The transformations are classified in chemical and enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of chemistry and biology.

Electron Transfer in Chemistry and Biology - The Primary Events in ...

Indian Academy of Sciences (India)

transfers, occurs in a cascade in many biological processes, including photosynthesis. ... the model reactions of photosynthetic ... biological relevance. GENERAL I ARTICLE of electrons, respectively. This has entirely changed the earlier framework of interpreting reactions in chemistry and biology. This shift in emphasis ...

Deep inelastic scattering near the Coulomb barrier

International Nuclear Information System (INIS)

Gehring, J.; Back, B.; Chan, K.

1995-01-01

Deep inelastic scattering was recently observed in heavy ion reactions at incident energies near and below the Coulomb barrier. Traditional models of this process are based on frictional forces and are designed to predict the features of deep inelastic processes at energies above the barrier. They cannot be applied at energies below the barrier where the nuclear overlap is small and friction is negligible. The presence of deep inelastic scattering at these energies requires a different explanation. The first observation of deep inelastic scattering near the barrier was in the systems 124,112 Sn + 58,64 Ni by Wolfs et al. We previously extended these measurements to the system 136 Xe + 64 Ni and currently measured the system 124 Xe + 58 Ni. We obtained better statistics, better mass and energy resolution, and more complete angular coverage in the Xe + Ni measurements. The cross sections and angular distributions are similar in all of the Sn + Ni and Xe + Ni systems. The data are currently being analyzed and compared with new theoretical calculations. They will be part of the thesis of J. Gehring

Developments in permeable and low permeability barriers

International Nuclear Information System (INIS)

Jefferis, S.A.; Norris, G.H.; Thomas, A.O.

1997-01-01

The concept of the reactive treatment zone whereby pollutants are attenuated as they move along a pathway in the ground has enabled a re-thinking of many of the concepts of containment. In particular it offers the potential for the control of the flux from a contaminated area by controlling the contaminant concentration in the pathway(s) as well as or instead of using a low permeability barrier. The paper outlines the basic concepts of the reactive treatment zone and the use of permeable and low permeability reactive systems. The paper then gives a case history of the installation of a permeable barrier using an in-situ reaction chamber

Coupled processes of fluid flow, solute transport, and geochemical reactions in reactive barriers

Energy Technology Data Exchange (ETDEWEB)

Kim, Jeongkon; Schwartz, Franklin W.; Xu, Tianfu; Choi, Heechul, and Kim, In S.

2004-01-02

A complex pattern of coupling between fluid flow and mass transport develops when heterogeneous reactions occur. For instance, dissolution and precipitation reactions can change a porous medium's physical properties, such as pore geometry and thus permeability. These changes influence fluid flow, which in turn impacts the composition of dissolved constituents and the solid phases, and the rate and direction of advective transport. Two-dimensional modeling studies using TOUGHREACT were conducted to investigate the coupling between flow and transport developed as a consequence of differences in density, dissolution precipitation, and medium heterogeneity. The model includes equilibrium reactions for aqueous species, kinetic reactions between the solid phases and aqueous constituents, and full coupling of porosity and permeability changes resulting from precipitation and dissolution reactions in porous media. In addition, a new permeability relationship is implemented in TOUGHREACT to examine the effects of geochemical reactions and density difference on plume migration in porous media. Generally, the evolutions in the concentrations of the aqueous phase are intimately related to the reaction-front dynamics. Plugging of the medium contributed to significant transients in patterns of flow and mass transport.

Conformational dependence of a protein kinase phosphate transfer reaction

Science.gov (United States)

Labute, Montiago; Henkelman, Graeme; Tung, Chang-Shung; Fenimore, Paul; McMahon, Ben

2007-03-01

Atomic motions and energetics for a phosphate transfer reaction catalyzed by the cAMP-dependent protein kinase have been calculated using plane-wave density functional theory, starting from structures of proteins crystallized in both the reactant conformation (RC) and the transition-state conformation (TC). In TC, we calculate that the reactants and products are nearly isoenergetic with a 20-kJ/mol barrier, whereas phosphate transfer is unfavorable by 120 kJ/mol in the RC, with an even higher barrier. Our results demonstrate that the phosphate transfer reaction occurs rapidly and reversibly in a particular conformation of the protein, and that the reaction can be gated by changes of a few tenths of an angstrom in the catalytic site [1]. [1] G.H. Henkelman, M.X. LaBute, C.-S. Tung, P.W. Fenimore, B.H. McMahon, Proc. Natl. Acad. Sci. USA vol. 102, no. 43:15347-15351 (2005).

Chemical interaction of tetravalent actinides simulators and the engineering barrier

International Nuclear Information System (INIS)

Chain, Pablo; Alba, Maria D.; Castro, Miguel A.; Pavon, Esperanza; Mar Orta, M.

2010-01-01

Document available in extended abstract form only. The Deep Geological Repository (DGR) is the most internationally accepted option for the storage of high radioactive wastes. This confinement is based on the Multi-barrier Concept where the engineered barrier is a crucial safety wise. Nowadays, bentonite is accepted as the best argillaceous material in the engineered barrier of DGR. Additionally to its well-known physical role, a chemical interaction between lutetium, as actinide simulator, and the smectite has been demonstrated. The existence of a reaction mechanism, which was not previously described, based on the chemical interaction between the lanthanide cations and the orthosilicate anions of the lamellar structure has been identified. This finding has aroused the interest of the scientific community because lanthanides are used as simulators of high activity radionuclide (HAR) in agreement with the guidelines established in the bibliography. It has been observed that in conditions of moderate temperature and pressure a chemical interaction exists between smectites and rare earth elements (RE) and phases of insoluble di-silicate, RE 2 Si 2 O 7 , which would immobilize RE, are generated. It is remarkable that the reaction extends to all the set of the smectites, although they do not display the same reactivity, the saponite being the most reactive. The main isotopes present in the HLW belong to the actinide elements Np, Pu, Am and Cm, in addition to uranium generated by neutron capture during the fuel combustion process. The study of the mobilization of actinide (IV) thorough the bentonite barrier is limited because of their radioactivity. However, U(IV), Np(IV), Pu(IV) and Th(IV) can be simulated by the stable isotopes of the Zr(IV) and Hf(IV), because they exhibit ionic radius and physicochemical properties very similar to those of the actinide elements. It is the main objective of this research to investigate the chemical interaction of Zr(IV) as actinide

Biological radiation effects

International Nuclear Information System (INIS)

Koggl, D.; Dedenkov, A.N.

1986-01-01

All nowadays problems of radio biology are considered: types of ionizing radiations, their interaction with material; damage of molecular structures and their reparation; reaction of cells and their recovery from radiation damage; reaction of the whole organism and its separate systems. Particular attention is given to the problems of radiation carcinogenesis and radiation hazard for man

Theoretical study of chain transfer to solvent reactions of alkyl acrylates.

Science.gov (United States)

Moghadam, Nazanin; Srinivasan, Sriraj; Grady, Michael C; Rappe, Andrew M; Soroush, Masoud

2014-07-24

This computational and theoretical study deals with chain transfer to solvent (CTS) reactions of methyl acrylate (MA), ethyl acrylate (EA), and n-butyl acrylate (n-BA) self-initiated homopolymerization in solvents such as butanol (polar, protic), methyl ethyl ketone (MEK) (polar, aprotic), and p-xylene (nonpolar). The results indicate that abstraction of a hydrogen atom from the methylene group next to the oxygen atom in n-butanol, from the methylene group in MEK, and from a methyl group in p-xylene by a live polymer chain are the most likely mechanisms of CTS reactions in MA, EA, and n-BA. Energy barriers and molecular geometries of reactants, products, and transition states are predicted. The sensitivity of the predictions to three hybrid functionals (B3LYP, X3LYP, and M06-2X) and three different basis sets (6-31G(d,p), 6-311G(d), and 6-311G(d,p)) is investigated. Among n-butanol, sec-butanol, and tert-butanol, tert-butanol has the highest CTS energy barrier and the lowest rate constant. Although the application of the conductor-like screening model (COSMO) does not affect the predicted CTS kinetic parameter values, the application of the polarizable continuum model (PCM) results in higher CTS energy barriers. This increase in the predicted CTS energy barriers is larger for butanol and MEK than for p-xylene. The higher rate constants of chain transfer to n-butanol reactions compared to those of chain transfer to MEK and p-xylene reactions suggest the higher CTS reactivity of n-butanol.

Reactions with Weakly Bound Nuclei, at near Barrier Energies, and the Breakup and Transfer Influences on the Fusion and Elastic Scattering

International Nuclear Information System (INIS)

Gomes, P. R. S.; Lubian, J.; Mendes-Junior, D. R.; Faria, P. N. de; Linares, R.; Sigaud, L.; Rangel, J.; Ferreira, J. L.; Paes, B.; Cardozo, E. N.; Cortes, M. R.; Canto, L. F.; Ermamatov, M. J.; Otomar, D. R.; Ferioli, E.; Lotti, P.; Hussein, M. S.

2016-01-01

We present a brief review of the reaction mechanisms involved in collisions of weakly bound projectiles with tightly bound targets, at near-barrier energies. We discuss systematic behaviors of the data, with emphasis in fusion, breakup, nucleon transfer and elastic scattering. The dependence of the breakup cross section on the charge and mass of the target is discussed, and the influence of the breakup channel on complete fusion is investigated. For this purpose, we compare reduced fusion cross sections with a benchmark universal curve. The behaviors observed in the comparisons are explained in terms of polarization potentials and of nucleon transfer followed by breakup. The influence of the breakup process on elastic scattering is also discussed. Some apparent contradictions between results of different authors are explained and some perspectives of the field are presented. (author)

In vitro models of the blood-brain barrier

DEFF Research Database (Denmark)

Helms, Hans Christian Cederberg; Abbott, N Joan; Burek, Malgorzata

2016-01-01

The endothelial cells lining the brain capillaries separate the blood from the brain parenchyma. The endothelial monolayer of the brain capillaries serves both as a crucial interface for exchange of nutrients, gases, and metabolites between blood and brain, and as a barrier for neurotoxic...... components of plasma and xenobiotics. This "blood-brain barrier" function is a major hindrance for drug uptake into the brain parenchyma. Cell culture models, based on either primary cells or immortalized brain endothelial cell lines, have been developed, in order to facilitate in vitro studies of drug...... transport to the brain and studies of endothelial cell biology and pathophysiology. In this review, we aim to give an overview of established in vitro blood-brain barrier models with a focus on their validation regarding a set of well-established blood-brain barrier characteristics. As an ideal cell culture...

Flexible barrier film, method of forming same, and organic electronic device including same

Science.gov (United States)

Blizzard, John; Tonge, James Steven; Weidner, William Kenneth

2013-03-26

A flexible barrier film has a thickness of from greater than zero to less than 5,000 nanometers and a water vapor transmission rate of no more than 1.times.10.sup.-2 g/m.sup.2/day at 22.degree. C. and 47% relative humidity. The flexible barrier film is formed from a composition, which comprises a multi-functional acrylate. The composition further comprises the reaction product of an alkoxy-functional organometallic compound and an alkoxy-functional organosilicon compound. A method of forming the flexible barrier film includes the steps of disposing the composition on a substrate and curing the composition to form the flexible barrier film. The flexible barrier film may be utilized in organic electronic devices.

Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

Science.gov (United States)

Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

2017-12-21

Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

Fusion of 6Li with 159Tb at near-barrier energies

International Nuclear Information System (INIS)

Pradhan, M. K.; Mukherjee, A.; Basu, P.; Goswami, A.; Kshetri, R.; Roy, Subinit; Chowdhury, P. Roy; Sarkar, M. Saha; Palit, R.; Parkar, V. V.; Santra, S.; Ray, M.

2011-01-01

Complete and incomplete fusion cross sections for 6 Li + 159 Tb have been measured at energies around the Coulomb barrier by the γ-ray method. The measurements show that the complete fusion cross sections at above-barrier energies are suppressed by ∼34% compared to coupled-channel calculations. A comparison of the complete fusion cross sections at above-barrier energies with the existing data for 11,10 B + 159 Tb and 7 Li + 159 Tb shows that the extent of suppression is correlated with the α separation energies of the projectiles. It has been argued that the Dy isotopes produced in the reaction 6 Li + 159 Tb at below-barrier energies are primarily due to the d transfer to unbound states of 159 Tb, while both transfer and incomplete fusion processes contribute at above-barrier energies.

Intramolecular kinetic isotope effect in gas-phase proton-transfer reactions

International Nuclear Information System (INIS)

Wellman, K.M.; Victoriano, M.E.; Isolani, P.C.; Riveros, J.M.

1979-01-01

The k/sub H//k/sub D/ isotope effects were determined by ICR for the reaction of substituted toluenes with several alkoxides. The results showed a definite trend for k/sub H//k/sub D/ starting as a normal isotope effect for appreciably exothermic reaction (> 3 kcal mol -1 ) and proceeding smoothly toward an inverse isotope effect as the reaction approached thermoneutrality or becomes endothermic. These observations were explained by a reaction which involved a double minima potential with a central energy barrier

Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier

Directory of Open Access Journals (Sweden)

Zhiling Liang

2018-01-01

Full Text Available The interactions (including weak interactions between dienophiles and dienes play an important role in the Diels-Alder reaction. To elucidate the influence of these interactions on the reactivity, a popular DFT functional and a variational DFT functional corrected with dispersion terms are used to investigate different substituent groups incorporated on the dienophiles and dienes. The bond order is used to track the trajectory of the cycloaddition reaction. The deformation/interaction model is used to obtain the interaction energy from the reactant complex to the inflection point until reaching the saddle point. The interaction energy initially increases with a decrease in the interatomic distance, reaching a maximum value, but then decreases when the dienophiles and dienes come closer. Reduced density gradient and chemical energy component analysis are used to analyse the interaction. Traditional transition state theory and variational transition state theory are used to obtain the reaction rates. The influence of tunneling on the reaction rate is also discussed.

Biological and Sociocultural Differences in Perceived Barriers to Physical Activity among 5th–7th Grade Urban Girls

Science.gov (United States)

Vermeesch, Amber L.; Ling, Jiying; Voskuil, Vicki R.; Bakhoya, Marion; Wesolek, Stacey M.; Bourne, Kelly A.; Pfeiffer, Karin A.; Robbins, Lorraine B.

2015-01-01

Background Inadequate physical activity (PA) contributes to the high prevalence of overweight and obesity among U.S. adolescent girls. Barriers preventing adolescent girls from meeting PA guidelines have not been thoroughly examined. Objectives The threefold purpose of this study was to: (a) determine pubertal stage, racial/ethnic, and socioeconomic status (SES) differences in ratings of interference of barriers to PA; (b) examine relationships between perceived barriers and age, body mass index (BMI), recreational screen time, sedentary activity, and PA; and (c) identify girls’ top-rated perceived barriers to PA. Methods Girls (N = 509) from eight Midwestern U.S. schools participated. Demographic, pubertal stage, perceived barriers, and recreational screen time data were collected via surveys. Height and weight were measured. Accelerometers measured sedentary activity, moderate-to-vigorous physical activity (MVPA), and light plus MVPA. Results Girls of low SES reported greater interference of perceived barriers to PA than those who were not of low SES (1.16 vs. 0.97, p = .01). Girls in early/middle puberty had lower perceived barriers than those in late puberty (1.03 vs. 1.24, p barriers were negatively related to MVPA (r = −.10, p = .03) and light plus MVPA (r = −.11, p = .02). Girls’ top five perceived barriers included lack of skills, hating to sweat, difficulty finding programs, being tired, and having pain. Discussion Innovative interventions, particularly focusing on skill development, are needed to assist girls in overcoming their perceived barriers to PA. PMID:26325276

Biological radiolesions and repair

International Nuclear Information System (INIS)

Laskowski, W.

1981-01-01

In 7 chapters, the book answers the following questions: 1) What reactions are induced in biological matter by absorption of radiation energy. 2) In what parts of the cell do the radiation-induced reactions with detectable biological effects occur. 3) In which way are these cell components changed by different qualities of radiation. 4) What are the cell mechanisms by which radiation-induced changes can be repaired. 5) What is the importance of these repair processes for man, his life and evolution. At the end of each chapter, there is a bibliography of relevant publications in this field. (orig./MG) [de

Reaction mechanism and spectroscopy of transfer reactions induced by heavy ions

International Nuclear Information System (INIS)

Lemaire, M.-C.

1977-01-01

The specific features displayed by data on heavy ion elastic and inelastic angular distributions are discussed, and their physical origin is pointed out from semi-classical calculations in counterpart ambiguities in the phenomenological description of the optical potential appear. Two nucleon transfer reactions induced by heavy ions successfully point out important contributions of a two-step process where the transfer is proceeding via target and residual nucleus inelastic excitation. At incident energies not too high above the Coulomb barrier, such process produces clear shape changes between different final state angular distributions. At higher incident energy, the angular distributions are forward peaked and display oscillations for both mechanisms. As for four-nucleon transfer reactions, the existing data suggest that the nucleons are well transferred into a Os relative

Heavy-ion optical potential for sub-barrier fusion deduced from a dispersion relation

International Nuclear Information System (INIS)

Kim, B.T.; Kim, H.C.; Park, K.E.

1988-01-01

The heavy-ion energy-dependent optical potentials for the 16 O+ 208 Pb system are deduced from a dispersion relation. These potentials are used to analyze the elastic scattering, fusion, and spin distributions of compound nuclei for the system in a unified way based on the direct reaction theory. It turns out that the energy dependence of the optical potential is essential in explaining the data at near- and sub-barrier energies. The real part of the energy-dependent optical potential deduced was also used in calculating the elastic and fusion cross sections by the conventional barrier penetration model using an incoming wave boundary condition. The predictions of the elastic scattering, fusion cross sections, and the spin distributions of compound nuclei are not satisfactory compared with those from the direct reaction approach. It seems to originate from the fact that this model neglects absorption around the Coulomb barrier region

Fission barriers of light nuclei

International Nuclear Information System (INIS)

Grotowski, K.; Planeta, R.; Blann, M.; Komoto, T.

1989-01-01

Experimental fission excitation functions for compound nuclei /sup 52/Fe, /sup 49/Cr, /sup 46/V, and /sup 44/Ti formed in heavy-ion reactions are analyzed in the Hauser-Feshbach/Bohr-Wheeler formalism using fission barriers based on the rotating liquid drop model of Cohen et al. and on the rotating finite range model of Sierk. We conclude that the rotating finite range approach gives better reproduction of experimental fission yields, consistent with results found for heavier systems

Dynamics of anion-molecule reactions at low energy

International Nuclear Information System (INIS)

Mikosch, J.

2007-11-01

Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S N 2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S N 2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S N 2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S N 2 mechanism involving CH 3 -rotation. (orig.)

Dynamics of anion-molecule reactions at low energy

Energy Technology Data Exchange (ETDEWEB)

Mikosch, J.

2007-11-15

Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S{sub N}2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S{sub N}2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S{sub N}2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S{sub N}2 mechanism involving CH{sub 3}-rotation. (orig.)

Claudins, dietary milk proteins, and intestinal barrier regulation.

Science.gov (United States)

Kotler, Belinda M; Kerstetter, Jane E; Insogna, Karl L

2013-01-01

The family of claudin proteins plays an important role in regulating the intestinal barrier by modulating the permeability of tight junctions. The impact of dietary protein on claudin biology has not been studied extensively. Whey proteins have been reported to improve intestinal barrier function, but their mechanism of action is not clear. Recent studies, however, have demonstrated increased intestinal claudin expression in response to milk protein components. Reviewed here are new findings suggesting that whey-protein-derived transforming growth factor β transcriptionally upregulates claudin-4 expression via a Smad-4-dependent pathway. These and other data, including limited clinical studies, are summarized below and, in the aggregate, suggest a therapeutic role for whey protein in diseases of intestinal barrier dysfunction, perhaps, in part, by regulating claudin expression. © 2013 International Life Sciences Institute.

Deuteron interaction with 124Sn nuclei at sub-barrier energies

Directory of Open Access Journals (Sweden)

Yu.N. Pavlenko

2015-04-01

Full Text Available The measurements of cross sections for deuteron elastic scattering and (d,p reaction on 124Sn nuclei have been performed with aim to study the features of sub-barrier deuteron interaction with heavy nuclei. Experimental data were obtained on the electrostatic Tandem accelerator EGP-10K of the Institute for Nuclear Research (Kyiv at the deuteron beam energies Ed = 4.0; 5.0 and 5.5 MeV. Cross sections of deuteron elastic scattering were calculated in approach where the deuteron interaction potential with heavy nuclei at sub-barrier energies has been constructed in the framework of single folding model using the complex dynamic polarization potential. It is shown that the account of finite deuteron size leads to the increasing the nuclear potential in outer region of interaction and significantly improves the description of the experimental data. The calculations of elastic scattering cross sections were performed without any variations of the nuclear potential parameters. The analysis of measured integral cross sections of the 124Sn(d,p reaction and calculated cross sections of deuteron breakup reaction 124Sn(d,pn124Sn shows the dominant contribution of the neutron transfer reaction in the processes of the formation of protons and elastic scattering cross sections.

Instantaneous Tunneling Flight Time for Wavepacket Transmission through Asymmetric Barriers.

Science.gov (United States)

Petersen, Jakob; Pollak, Eli

2018-04-12

The time it takes a particle to tunnel through the asymmetric Eckart barrier potential is investigated using Gaussian wavepackets, where the barrier serves as a model for the potential along a chemical reaction coordinate. We have previously shown that the, in principle experimentally measurable, tunneling flight time, which determines the time taken by the transmitted particle to traverse the barrier, vanishes for symmetric potentials like the Eckart and square barrier [ Petersen , J. ; Pollak , E. J. Phys. Chem. Lett. 2017 , 9 , 4017 ]. Here we show that the same result is obtained for the asymmetric Eckart barrier potential, and therefore, the zero tunneling flight time seems to be a general result for one-dimensional time-independent potentials. The wavepacket dynamics is simulated using both an exact quantum mechanical method and a classical Wigner prescription. The excellent agreement between the two methods shows that quantum coherences are not important in pure one-dimensional tunneling and reinforces the conclusion that the tunneling flight time vanishes.

Inner ear barriers to nanomedicine-augmented drug delivery and imaging

Directory of Open Access Journals (Sweden)

Jing Zou

2016-12-01

Full Text Available There are several challenges to inner ear drug delivery and imaging due to the existence of tight biological barriers to the target structure and the dense bone surrounding it. Advances in imaging and nanomedicine may provide knowledge for overcoming the existing limitations to both the diagnosis and treatment of inner ear diseases. Novel techniques have improved the efficacy of drug delivery and targeting to the inner ear, as well as the quality and accuracy of imaging this structure. In this review, we will describe the pathways and biological barriers of the inner ear regarding drug delivery, the beneficial applications and limitations of the imaging techniques available for inner ear research, the behavior of engineered nanomaterials in inner ear applications, and future perspectives for nanomedicine-based inner ear imaging.

Reaction of Pentanol isomers with OH radical – A theoretical perspective

Science.gov (United States)

Aazaad, Basheer; Lakshmipathi, Senthilkumar

2018-05-01

The stability of all the three isomeric forms of Pentanol has been examined with relative energy analysis. Even though 2-Pentanol is predicted to be most stable isomeric form, all the three isomeric forms undergo hydrogen atom abstraction reaction with OH radical. Among the proposed 18 different hydrogen atom abstraction reaction, the abstraction from CH2 and CH functional group is found to be a favourable reactive site with low energy barrier in M06-2X/6-311+G(d,p) level of theory. Wiberg bond order analysis shows all the abstraction reactions are concreted but not synchronic in nature. Using force analysis, the calculated work done of individual reaction regions illustrates that structural rearrangements drive the reaction with higher contribution to the energy barrier. The rate constant calculated at M06-2X method for the most favourable reaction is well matched with available experimental data. Using the reported atmospheric OH concentration (1 × 106 molecules/cm3), the life time of 1-Pentanol, 2-Pentanol and 3-Pentanol has calculated to be 18.66, 0.36 and 2.86 days, respectively.

Dynamics of {sup 40,48}Ca+{sup 238}U→{sup 278,286}112{sup ⁎} reactions across the Coulomb barrier using dynamical cluster decay model

Energy Technology Data Exchange (ETDEWEB)

Sandhu, Kirandeep; Kaur, Gurvinder; Sharma, Manoj K., E-mail: msharma@thapar.edu

2014-01-15

The role of deformations and related orientations (optimum or compact) is investigated in reference to dynamics of {sup 40,48}Ca+{sup 238}U→{sup 278,286}112{sup ⁎} reactions using dynamical cluster decay model (DCM). The use of quadrupole and hexadecapole deformations in the decay of compound system suggest that the degree of compactness changes with addition of higher order deformations. The decay cross-sections are calculated in reference to the available data, including β{sub 2}-static deformations within ‘optimum’ orientation approach. The comparative analysis of spherical, β{sub 2}-static and dynamic alongwith β{sub 4}-static deformations is investigated at comparable center of mass energy of 230 MeV for both nuclei. To address the specific role of optimized orientations in the decay of {sup 278}112{sup ⁎} and {sup 286}112{sup ⁎} nuclei, the calculations are done using equatorial compact and polar elongated orientations. Using hot equatorial collisions, symmetric fission is observed as the dominant decay mode across the barrier, which otherwise becomes asymmetric for cold elongated approach. The calculated cross-sections match nicely with experimental data using hot configuration but the same are overestimated for the use of cold (polar) orientation approach at deep sub-barrier region. This overestimation in the deep sub-barrier region may be associated with the quasi-fission decay channel. The contribution of QF in both {sup 278}112{sup ⁎} and {sup 286}112{sup ⁎} nuclei are predicted through the overestimated cross-sections being more for neutron-deficient {sup 278}112{sup ⁎} nucleus, in agreement with experimental results. Larger barrier modification ΔV{sub B} is observed at sub-barrier energies for both isotopes of Z=112 nucleus. Also the contribution of ΔV{sub B} at lower incident energies is relatively higher for cold elongated polar configuration as compared to hot compact equatorial configuration, causing overestimation of cross

Estimation of the reaction efficiency in polymerase chain reaction

NARCIS (Netherlands)

Lalam, N.

2006-01-01

Polymerase chain reaction (PCR) is largely used in molecular biology for increasing the copy number of a specific DNA fragment. The succession of 20 replication cycles makes it possible to multiply the quantity of the fragment of interest by a factor of 1 million. The PCR technique has

Application of biological barriers in maintaining the integrity of radioactivity in shallow burial grounds

International Nuclear Information System (INIS)

Cline, J.F.

1979-05-01

Stabilization of a shallow burial site requires some means of keeping buried radioactive wastes in place and preventing the movement of radioactive elements into the biosphere by various vectors present in the soil covering the burial site. By placing a barrier between the surface of the soil and the buried wastes, it would be possible to isolate the wastes from the biosphere and eliminate the movement of radioactive elements into the environment. An effective biobarrier would make it possible to grow plants over the buried wastes regardless of rooting habits; the plants would stabilize the surface soil, prevent wind erosion, and transpire soil water back into the air, thus preventing it from percolating downward through the buried wastes. This report summarizes the finding of a study undertaken to determine the effectiveness of natural cobblestones as a long-term biobarrier. In the initial field study, we investigated whether a thick layer of cobblestones would prevent plant roots and burrowing animals from reaching contaminated materials and transferring radionuclides to the soil surface. In a subsequent greenhouse study, three modifications of the cobblestone barrier were tested, including the addition of another layer of stones, one of asphalt, and one of a root toxin. These data show that cobblestone can be effective as a barrier to burrowing animals and insects, but not totally effective as a barrier to plant roots. Because of variable weather patterns at Hanford, five to six year studies are recommended for further studies on the effectiveness of different materials as biobarriers to radioactive substances. Stone size appeared to affect the plants' rate of root growth since root growth slowed in the air spaces between stones. Root toxin was 100% effective as a means of keeping roots out of the buried waste; this method could be used as a barrier modification where no plant cover is needed

Natural physical and biological processes compromise the long-term performance of compacted soil caps

International Nuclear Information System (INIS)

Smith, E.D.

1995-01-01

Compacted soil barriers are components of essentially all caps placed on closed waste disposal sites. The intended functions of soil barriers in waste facility caps include restricting infiltration of water and release of gases and vapors, either independently or in combination with synthetic membrane barriers, and protecting other manmade or natural barrier components. Review of the performance of installed soil barriers and of natural processes affecting their performance indicates that compacted soil caps may function effectively for relatively short periods (years to decades), but natural physical and biological processes can be expected to cause them to fail in the long term (decades to centuries). This paper addresses natural physical and biological processes that compromise the performance of compacted soil caps and suggests measures that may reduce the adverse consequences of these natural failure mechanisms

Systematic analysis of above-barrier fusion of 9,10,11Be+209Bi

International Nuclear Information System (INIS)

Hinde, D. J.; Dasgupta, M.

2010-01-01

Measurements of fusion for 9,10,11 Be allow testing of the relative importance to fusion and breakup of the α-cluster structure found in all these Be isotopes, compared with the neutron-halo structure only present for 11 Be. However, disagreements exist among different published experimental data sets for the reactions of 9,10,11 Be with 209 Bi. Accurate measurements of above-barrier cross sections for the products of complete fusion (fission and evaporation residues) in the reaction of 9 Be with 209 Bi and 208 Pb provide the basis for a reanalysis of above-barrier fusion for 10,11 Be+ 209 Bi. This includes procedures making full use of the higher precision stable beam data and resolves many of the disagreements. The improved self-consistency of the analysis allows investigation of the experimental average fusion barriers. Although showing some scatter, these suggest a higher barrier for the neutron halo nucleus 11 Be. Comparison of published cross sections for fusion associated with capture of all the charge of the projectile suggest that all these Be isotopes show significant suppression of complete fusion, a surprising result given that the α-breakup threshold energies are 1.57 MeV for 9 Be but over 7 MeV for 10,11 Be. Further experimental studies to investigate in more detail the division between complete and incomplete fusion for reactions of 10,11 Be are needed.

Knowledge of Adverse Drug Reaction Reporting and the Pharmacovigilance of Biological Medicines: A Survey of Healthcare Professionals in Ireland.

Science.gov (United States)

O'Callaghan, J; Griffin, B T; Morris, J M; Bermingham, Margaret

2018-06-01

In Europe, changes to pharmacovigilance legislation, which include additional monitoring of medicines, aim to optimise adverse drug reaction (ADR) reporting systems. The legislation also makes provisions related to the traceability of biological medicines. The objective of this study was to assess (i) knowledge and general experience of ADR reporting, (ii) knowledge, behaviours, and attitudes related to the pharmacovigilance of biologicals, and (iii) awareness of additional monitoring among healthcare professionals (HCPs) in Ireland. Hospital doctors (n = 88), general practitioners (GPs) (n = 197), nurses (n = 104) and pharmacists (n = 309) completed an online questionnaire. There were differences in mean knowledge scores relating to ADR reporting and the pharmacovigilance of biologicals among the HCP groups. The majority of HCPs who use biological medicines in their practice generally record biologicals by brand name but practice behaviours relating to batch number recording differed between some professions. HCPs consider batch number recording to be valuable but also regard it as being more difficult than brand name recording. Most respondents were aware of the concept of additional monitoring but awareness rates differed between some groups. Among those who knew about additional monitoring, there was higher awareness of the inverted black triangle symbol among pharmacists (> 86.4%) compared with hospital doctors (35.1%), GPs (35.6%), and nurses (14.9%). Hospital pharmacists had more experience and knowledge of ADR reporting than other practising HCPs. This study highlights the important role hospital pharmacists play in post-marketing surveillance. There is a need to increase pharmacovigilance awareness of biological medicines and improve systems to support their batch traceability.

Integrated Biological Control

International Nuclear Information System (INIS)

JOHNSON, A.R.

2002-01-01

Biological control is any activity taken to prevent, limit, clean up, or remediate potential environmental, health and safety, or workplace quality impacts from plants, animals, or microorganisms. At Hanford the principal emphasis of biological control is to prevent the transport of radioactive contamination by biological vectors (plants, animals, or microorganisms), and where necessary, control and clean up resulting contamination. Other aspects of biological control at Hanford include industrial weed control (e.g.; tumbleweeds), noxious weed control (invasive, non-native plant species), and pest control (undesirable animals such as rodents and stinging insects; and microorganisms such as molds that adversely affect the quality of the workplace environment). Biological control activities may be either preventive (apriori) or in response to existing contamination spread (aposteriori). Surveillance activities, including ground, vegetation, flying insect, and other surveys, and apriori control actions, such as herbicide spraying and placing biological barriers, are important in preventing radioactive contamination spread. If surveillance discovers that biological vectors have spread radioactive contamination, aposteriori control measures, such as fixing contamination, followed by cleanup and removal of the contamination to an approved disposal location are typical response functions. In some cases remediation following the contamination cleanup and removal is necessary. Biological control activities for industrial weeds, noxious weeds and pests have similar modes of prevention and response

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

Science.gov (United States)

Kojima, H.; Yamada, A.; Okazaki, S.

2015-05-01

The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

Fusion dynamics of 2020Ne + 20882Pb reaction using static and energy dependent Woods-Saxon potential

International Nuclear Information System (INIS)

Gautam, Manjeet Singh; Kaur, Amandeep; Sharma, Manoj K.

2015-01-01

The present work compares the theoretical predictions based on static Woods-Saxon potential and the EDWSP model along with one dimensional Wong formula. For 20 20 Ne + 208 82 Pb reaction, the theoretical calculations obtained by using static Woods-Saxon potential are substantially smaller than that of experimental data at below barrier energies and explain the fusion data at above barrier energies only. On the other hand, the EDWSP model based calculations adequately describe the observed fusion enhancement of 20 20 Ne + 208 82 Pb reaction in whole range of energy spread across the Coulomb barrier. Furthermore, a wide range of the diffuseness parameter ranging from 0.96 fm to 0.85 fm is required to address the sub-barrier fusion data

Deep inelastic scattering near the Coulomb barrier

Energy Technology Data Exchange (ETDEWEB)

Gehring, J.; Back, B.; Chan, K. [and others

1995-08-01

Deep inelastic scattering was recently observed in heavy ion reactions at incident energies near and below the Coulomb barrier. Traditional models of this process are based on frictional forces and are designed to predict the features of deep inelastic processes at energies above the barrier. They cannot be applied at energies below the barrier where the nuclear overlap is small and friction is negligible. The presence of deep inelastic scattering at these energies requires a different explanation. The first observation of deep inelastic scattering near the barrier was in the systems {sup 124,112}Sn + {sup 58,64}Ni by Wolfs et al. We previously extended these measurements to the system {sup 136}Xe + {sup 64}Ni and currently measured the system {sup 124}Xe + {sup 58}Ni. We obtained better statistics, better mass and energy resolution, and more complete angular coverage in the Xe + Ni measurements. The cross sections and angular distributions are similar in all of the Sn + Ni and Xe + Ni systems. The data are currently being analyzed and compared with new theoretical calculations. They will be part of the thesis of J. Gehring.

Temperature dependence of muonium reaction rates in the gas phase

International Nuclear Information System (INIS)

Fleming, D.G.; Garner, D.M.; Mikula, R.J.; British Columbia Univ., Vancouver

1981-01-01

A study of the temperature dependence of reaction rates has long been an important tool in establishing reaction pathways in chemical reactions. This is particularly true for the reactions of muonium (in comparison with those of hydrogen) since a measurement of the activation energy for chemical reaction is sensitive to both the height and the position of the potential barrier in the reaction plane. For collision controlled reactions, on the other hand, the reaction rate is expected to exhibit a weak T 1 sup(/) 2 dependence characteristic of the mean collision velocity. These concepts are discussed and their effects illustrated in a comparison of the chemical and spin exchange reaction rates of muonium and hydrogen in the temperature range approx.300-approx.500 K. (orig.)

Quantum chemical study of the elementary reactions in zirconium oxide atomic layer deposition

International Nuclear Information System (INIS)

Widjaja, Yuniarto; Musgrave, Charles B.

2002-01-01

Elementary reactions in atomic layer deposition of zirconia using zirconium tetrachloride and water are investigated using the density functional theory. The atomistic mechanisms of the two deposition half cycles on the Zr-OH and Zr-Cl surface sites are investigated. Both half reactions proceed through the formation of stable intermediates, resulting in high barriers for HCl formation. We find that the intermediate stability is lowered as the surface temperature is raised. However, increasing temperature also increases the dissociation free-energy barrier, which in turn results in increased desorption of adsorbed precursors

Long term performance of the Waterloo denitrification barrier

International Nuclear Information System (INIS)

Robertson, W.D.; Cherry, J.A.

1997-01-01

Beginning in 1991 a series of laboratory tests and small scale field trials were initiated to test the performance of an innovative permeable reactive barrier for treatment of nitrate from septic systems. The barrier promotes denitrification by providing an energy source in the form of solid organic carbon mixed into the porous media material. Advantages of the system for nitrate treatment are that the reaction is passive and in situ and it is possible to incorporate sufficient carbon mass in conveniently sized barriers to potentially provide treatment for long periods (decades) without the necessity for maintenance. However, longevity can only be demonstrated by careful long term monitoring of field installations. This paper documents four years of operating history at three small scale field trials; two where the denitrification barrier is installed as a horizontal layer positioned in the unsaturated zone below conventional septic system infiltration beds and one where the barrier is installed as a vertical wall intercepting a septic system plume at a downgradient location. The barriers have successfully attenuated 50-100% of NO - 3 -N levels of up to 170 mg/L and treatment has remained consistent over the four year period in each case, thus considerable longevity is indicated. Other field trials have demonstrated this technology to be equally effective in treating nitrogen contamination from other sources such as landfill leachate and farm field runoff

Synthesis of porous gold nanoshells by controlled transmetallation reaction

Energy Technology Data Exchange (ETDEWEB)

Pattabi, Manjunatha, E-mail: manjupattabi@yahoo.com; M, Krishnaprabha [Department of Materials Science, Mangalore University, Mangalagangothri-574199 (India)

2015-06-24

Aqueous synthesis of porous gold nanoshells in one step is carried out through controlled transmetallation (TM) reaction using a naturally available egg shell membrane (ESM) as a barrier between the sacrificial silver particles (AgNPs) and the gold precursor solution (HAuCl{sub 4}). The formation of porous gold nanoshells via TM reaction is inferred from UV-Vis spectroscopy and the scanning electron microscopic (SEM) studies.

Strategies to improve drug delivery across the blood-brain barrier.

Science.gov (United States)

de Boer, Albertus G; Gaillard, Pieter J

2007-01-01

The blood-brain barrier (BBB), together with the blood-cerebrospinal-fluid barrier, protects and regulates the homeostasis of the brain. However, these barriers also limit the transport of small-molecule and, particularly, biopharmaceutical drugs such as proteins, genes and interference RNA to the brain, thereby limiting the treatment of many brain diseases. As a result, various drug delivery and targeting strategies are currently being developed to enhance the transport and distribution of drugs into the brain. In this review, we discuss briefly the biology and physiology of the BBB as the most important barrier for drug transport to the brain and, in more detail, the possibilities for delivering large-molecule drugs, particularly genes, by receptor-mediated nonviral drug delivery to the (human) brain. In addition, the systemic and intracellular pharmacokinetics of nonviral gene delivery, together with targeted brain imaging, are reviewed briefly.

Examining barrier distributions and, in extension, energy derivative of probabilities for surrogate experiments

International Nuclear Information System (INIS)

Romain, P.; Duarte, H.; Morillon, B.

2012-01-01

The energy derivatives of probabilities are functions suited to a best understanding of certain mechanisms. Applied to compound nuclear reactions, they can bring information on fusion barrier distributions as originally introduced, and also, as presented here, on fission barrier distributions and heights. Extendedly, they permit to access the compound nucleus spin-parity states preferentially populated according to an entrance channel, at a given energy. (authors)

Non extensive corrections to stellar nuclear reactions rate

Energy Technology Data Exchange (ETDEWEB)

Assuncao, M. [Universidade Federal de Sao Paulo (DCET/UNIFESP), Diadema, SP (Brazil). Dept. de Ciencias Exatas e da Terra; Silveira, F.E.M. [Universidade Federal do ABC, Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas; Lima, J.A.S. [Universidade de Sao Paulo (IAG/USP), SP (Brazil). Inst. de Astronomia, Geofisica e Ciencias Atmosfericas

2010-07-01

Full text: Stellar nucleosynthesis is widely accepted as the basic mechanism for creation of chemical elements in the Universe. In particular, nuclear reactions occurring in the Sun are recognized as responsible for its energy generation. The problem of to determine the energy generation mechanism in stars was firstly attacked by Gamow in the framework of his quantum mechanical theory of potential barrier penetration. According to that approach, the reactions rate is calculated by averaging the penetration factor over the velocity distribution of the plasma particles. A randomization of that distribution is expected as a consequence of the reactions. However, diffusion processes in the macroscopic environment should balance the resulting particles number depletion. Therefore, matter, energy, and momentum might steadily flow. In other words, a quasi-stationary equilibrium state must be attained. In this work, the potential barrier penetration approach to stellar nuclear reactions rate has been rediscussed with basis on Tsallis nonextensive statistics. The investigation has been restricted to non-resonant reactions, for which the S-factor can be regarded as a constant. It has been found that, within the extended formulation, the nonextensive q-parameter is constrained to a maximum value. Accordingly, the q-energy has been shown to exhibit a minimum. The q-Gamow peak has been derived and, in connection with the usual Gaussian approximation, the corresponding half q-width has been also estimated. Plots of the q-energy, q-Gamow peak and half q-width for some reactions with stellar physics interest have been produced. (author)

Benzene destruction in claus process by sulfur dioxide: A reaction kinetics study

KAUST Repository

Sinha, Sourab; Raj, Abhijeet Dhayal; Alshoaibi, Ahmed S.; Alhassan, Saeed M.; Chung, Suk-Ho

2014-01-01

interactions. The mechanism begins with SO2 addition to phenyl radical after overcoming an energy barrier of 6.4 kJ/mol. This addition reaction is highly exothermic, where a reaction energy of 182 kJ/mol is released. The most favorable pathway involves O-S bond

The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

2010-01-01

We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

Drug and xenobiotic biotransformation in the blood-brain barrier: A neglected issue.

Directory of Open Access Journals (Sweden)

José A.G. Agúndez

2014-10-01

Full Text Available Drug biotransformation is a crucial mechanism for facilitating the elimination of chemicals from the organism and for decreasing their pharmacological activity. Published evidence suggests that brain drug metabolism may play a role in the development of adverse drug reactions and in the clinical response to drugs and xenobiotics. The blood-brain barrier (BBB has been regarded mainly as a physical barrier for drugs and xenobiotics, and little attention has been paid to BBB as a drug-metabolizing barrier. The presence of drug metabolizing enzymes in the BBB is likely to have functional implications because local metabolism may inactivate drugs or may modify the drug's ability to cross the BBB, thus modifying the drug response and the risk of developing adverse drug reactions. In this perspective paper, we discuss the expression of relevant xenobiotic metabolizing enzymes in the brain and in the BBB, and we cover current advances and future directions on the potential role of these BBB drug-metabolizing enzymes as modifiers of drug response.

Symmetric fusion of heavy ions around the Coulomb barrier energy

International Nuclear Information System (INIS)

Royer, G.; Remaud, B.

1983-01-01

Using the liquid drop model, we have performed a systematic study of the symmetric fusion with a neck degree of freedom and tunnelling effects, the nuclear potential being calculated with the proximity approach. Barrier heights and positions are in very good agreement with experimental data when they are known (light-medium systems); the recent experimental data of the reactions 58 Ni + 58 Ni and 64 Ni + 64 Ni are particularly investigated. For heavier systems double-humped fusion barriers and isomeric states are predicted which strongly limit the complete fusion probability

CO2 valorization by means of Dielectric Barrier Discharge

Science.gov (United States)

Machrafi, H.; Cavadias, S.; Amouroux, J.

2011-01-01

As atmospheric pollution is causing several environmental problems it is incumbent to reduce the impact of pollution on the environment. One particular problem is the production of CO2 by many transport and industrial applications. Instead of stocking CO2 and instead of being a product, it can be used as a source. The case considered is the CO2 reformation of methane producing hydrogen and CO. It is an endothermic reaction, for which the activation barrier needs to be surpassed. This can be done efficiently by the method of Dielectric Barrier Discharge. The process relies on the collision of electrons, which are accelerated under an electrical field that is created in the discharge area. This leads to the formation of reactive species, which facilitate the abovementioned reaction. This study is performed using a Matlab program with the Reaction Engineering module in COMSOL (with an incorporated kinetic mechanism) in order to model the discharge phase. Then COMSOL (continuity and Navier-Stokes equations) is used to model the flow in the post-discharge phase. The results showed that both a 2D and 3D model can be used to model the chemical-plasma process. These methods need strongly reduced kinetic mechanism, which in some cases can cause loss of precision.

CO2 valorization by means of Dielectric Barrier Discharge

International Nuclear Information System (INIS)

Machrafi, H; Cavadias, S; Amouroux, J

2011-01-01

As atmospheric pollution is causing several environmental problems it is incumbent to reduce the impact of pollution on the environment. One particular problem is the production of CO 2 by many transport and industrial applications. Instead of stocking CO 2 and instead of being a product, it can be used as a source. The case considered is the CO 2 reformation of methane producing hydrogen and CO. It is an endothermic reaction, for which the activation barrier needs to be surpassed. This can be done efficiently by the method of Dielectric Barrier Discharge. The process relies on the collision of electrons, which are accelerated under an electrical field that is created in the discharge area. This leads to the formation of reactive species, which facilitate the abovementioned reaction. This study is performed using a Matlab program with the Reaction Engineering module in COMSOL (with an incorporated kinetic mechanism) in order to model the discharge phase. Then COMSOL (continuity and Navier-Stokes equations) is used to model the flow in the post-discharge phase. The results showed that both a 2D and 3D model can be used to model the chemical-plasma process. These methods need strongly reduced kinetic mechanism, which in some cases can cause loss of precision.

Diels-Alder reactions onto fluorinated and hydrogenated graphene

Science.gov (United States)

Denis, Pablo A.

2017-09-01

We studied Diels-Alder (DA) reactions onto functionalized graphene. When fluorine, hydrogen or oxygen functional groups are present on one side of the sheet, the DA cycloadditions become significantly more exergonic when performed on the opposite side. Hydrogen is more effective than fluorine and oxygen to promote these cycloadditions. In contrast with the results obtained for perfect graphene, the functionalization with H, F or O turns the DA reactions exergonic, with ΔG°298 = -127.2 kcal/mol. The reaction barriers are expected to be considerably lowered with respect to perfect graphene because the functional groups significantly reduce the distortion energy.

The Pictet-Spengler reaction in solid-phase combinatorial chemistry

DEFF Research Database (Denmark)

Nielsen, Thomas E; Diness, Frederik; Meldal, Morten

2003-01-01

The Pictet-Spengler reaction is an important reaction for the generation of tetrahydro-beta-carbolines and tetrahydroisoquinoline ring systems, which exhibit a range of biological and pharmacological properties. This review covers the solid-phase Pictet-Spengler reaction, as employed in solid...

Stochastic semi-classical description of sub-barrier fusion reactions

Directory of Open Access Journals (Sweden)

Ayik Sakir

2011-10-01

Full Text Available A semi-classical method that incorporates the quantum effects of the low-lying vibrational modes is applied to fusion reactions. The quantum effect is simulated by stochastic sampling of initial zero-point fluctuations of the surface modes. In this model, dissipation of the relative energy into non-collective excitations of nuclei can be included straightforwardly. The inclusion of dissipation is shown to increase the agreement with the fusion cross section data of Ni isotopes.

Aging and Phase Stability of Waste Package Outer Barrier

Energy Technology Data Exchange (ETDEWEB)

Tammy S. Edgecumble Summers

2001-08-23

This Analysis Model Report (AMR) was prepared in accordance with the Work Direction and Planning Document, ''Aging and Phase Stability of Waste Package Outer Barrier'' (CRWMS M&O 1999a). ICN 01 of this AMR was developed following guidelines provided in TWP-MGR-MD-000004 REV 01, ''Technical Work Plan for: Integrated Management of Technical Product Input Department'' (BSC 2001, Addendum B). It takes into consideration the Enhanced Design Alternative II (EDA II), which has been selected as the preferred design for the Engineered Barrier System (EBS) by the License Application Design Selection (LADS) program team (CRWMS M&O 1999b). The salient features of the EDA II design for this model are a waste package (WP) consisting of an outer barrier of Alloy 22 and an inner barrier of Type 316L stainless steel. This report provides information on the phase stability of Alloy 22l, the current waste-package-outer-barrier (WPOB) material. These phase stability studies are currently divided into three general areas: (1) Long-range order reactions; (2) Intermetallic and carbide precipitation in the base metal; and (3) Intermetallic and carbide precipitation in welded samples.

Detailed determination of the fusion nuclear radius in reactions involving weakly bound projectiles

International Nuclear Information System (INIS)

Gomez Camacho, A.; Aguilera, E. F.; Quiroz, E. M.

2007-01-01

A detailed determination of the fusion radius parameter is performed within the Distorted Wave Born Approximation for reactions involving weakly bound projectiles. Specifically, a simultaneous X 2- analysis of elastic and fusion cross section data is done using a Woods-Saxon potential with volume and surface parts. The volume part is assumed to be responsible for fusion reactions while the surface part for all other direct reactions. It is proved that in order to fit fusion data, particularly for energies below the Coulomb barrier where fusion is enhanced, it is necessary to have a value of around 1.4 fm for the fusion radial parameter of the fusion potential (W F ). This value is much higher than that frequently used in Barrier Penetration models (1.0 fm). The calculations are performed for reactions involving the weakly bound projectile 9 Be with several medium mass targets. (Author)

Recombination barrier layers in solid-state quantum dot-sensitized solar cells

KAUST Repository

Roelofs, Katherine E.

2012-06-01

By replacing the dye in the dye-sensitized solar cell design with semiconductor quantum dots as the light-absorbing material, solid-state quantum dot-sensitized solar cells (ss-QDSSCs) were fabricated. Cadmium sulfide quantum dots (QDs) were grown in situ by successive ion layer adsorption and reaction (SILAR). Aluminum oxide recombination barrier layers were deposited by atomic layer deposition (ALD) at the TiO2/hole-conductor interface. For low numbers of ALD cycles, the Al2O3 barrier layer increased open circuit voltage, causing an increase in device efficiency. For thicker Al2O3 barrier layers, photocurrent decreased substantially, leading to a decrease in device efficiency. © 2012 IEEE.

Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

KAUST Repository

Zhang, Xuming; Cha, Min

2015-01-01

We studied the relative importance of the reduced field intensity and the background reaction temperature in the partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor. We obtained important mechanistic insight

Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

Energy Technology Data Exchange (ETDEWEB)

Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

2016-12-05

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

Delivery of Biologics Across the Blood-Brain Barrier Through Nanoencapsulation

DEFF Research Database (Denmark)

Bruun, Jonas

is a polymeric micelle made from an anionic triblock copolymer and was intended for delivery of drugs to the central nervous system (CNS), which is protected by the largely impermeable blood-brain barrier (BBB). In order to target the nanocarrier to the brain endothelial cells and obtain receptor...... of the reporter protein. One of the great challenges for drug delivery by nanocarriers is the dilemma of designing a particle that is highly stable whit no cellular interaction while in the blood stream but has a high uptake and efficient drug release in the diseased cells. As a solution to this dilemma...

Application of polycrystalline diffusion barriers

International Nuclear Information System (INIS)

Tsymbal, V.A.; Kolupaev, I.N.

2010-01-01

Degradation of contacts of the electronic equipment at the raised temperatures is connected with active diffusion redistribution of components contact - metalized systems (CMS) and phase production on interphase borders. One of systems diffusion barriers (DB) are polycrystalline silicide a film, in particular silicides of the titan. Reception disilicide the titan (TiSi 2 ) which on the parameters is demanded for conditions of microelectronics from known silicides of system Ti-Si, is possible as a result of direct reaction of a film of the titan and a substrate of silicon, and at sedimentation of layer Ti-Si demanded stoichiometric structure. Simultaneously there is specific problem polycrystalline diffusion a barrier (PDB): the polycrystalline provides structural balance and metastability film disilicide, but leaves in it borders of grains - easy local ways of diffusion. In clause the analysis diffusion permeability polycrystalline and polyphase DB is made and recommendations for practical methods of increase of blocking properties PDB are made.

Performance of the diffusion barrier in the metallic fuel in sodium-cooled fast reactor

International Nuclear Information System (INIS)

Kim, Jun Hwan; Ryu, Ho Jin; Yang, Seong Woo; Lee, Byoung Oon; Oh, Seok Jin; Lee, Chan Bock; Hahn, Dohee

2009-01-01

The objectives in this study are to propose several kinds of barrier materials and to evaluate their performance to prevent a fuel-clad interaction situation between the metallic fuel and the clad material in the Sodium-cooled Fast Reactor (SFR). Metallic foil made from refractory element, electrodeposition of the Cr on the clad surface, and the vapor deposition of the Zr were used as the barrier layers. The diffusion couple test was performed at the temperature of 800degC for 25 hour. The results showed that considerable amount of reaction occurred at the specimen without barrier, whereas excellent performance was observed in that neither reaction nor inter-diffusion occurred in the case of metallic foil made of Cr or V. Electrodeposition was revealed to be excellent provided that optimum deposition condition can be found. Similar to the electro-deposition result, excellent performance observed in the case of vapor deposition condition. (author)

GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

Energy Technology Data Exchange (ETDEWEB)

Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayon, Victor M.; Largo, Antonio, E-mail: alargo@qf.uva.es [Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain)

2012-04-01

A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol{sup -1} at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH{sub 3}OH{sup +}, with acetic acid also involves a high barrier (more than 27 kcal mol{sup -1} at the CCSD(T) level). Only the higher energy isomer, NH{sub 2}OH{sup +}{sub 2}, leads to a sensibly lower energy barrier (about 2.3 kcal mol{sup -1} at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

International Nuclear Information System (INIS)

Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayón, Víctor M.; Largo, Antonio

2012-01-01

A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol –1 at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH 3 OH + , with acetic acid also involves a high barrier (more than 27 kcal mol –1 at the CCSD(T) level). Only the higher energy isomer, NH 2 OH + 2 , leads to a sensibly lower energy barrier (about 2.3 kcal mol –1 at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

SABIO-RK: A data warehouse for biochemical reactions and their kinetics

Directory of Open Access Journals (Sweden)

Krebs Olga

2007-03-01

Full Text Available Systems biology is an emerging field that aims at obtaining a system-level understanding of biological processes. The modelling and simulation of networks of biochemical reactions have great and promising application potential but require reliable kinetic data. In order to support the systems biology community with such data we have developed SABIO-RK (System for the Analysis of Biochemical Pathways - Reaction Kinetics, a curated database with information about biochemical reactions and their kinetic properties, which allows researchers to obtain and compare kinetic data and to integrate them into models of biochemical networks. SABIO-RK is freely available for academic use at http://sabio.villa-bosch.de/SABIORK/.

How does the carbon fusion reaction happen in stars?

International Nuclear Information System (INIS)

Tang, X.; Bucher, B.; Fang, X.; Notani, M.; Tan, W.P.; Mooney, P.; Li, Y.; Esbensen, H.; Jiang, C.L.; Rehm, K.E.; Lin, C.J; Brown, E.

2012-01-01

The 12 C + 12 C fusion reaction is one of the most important reactions in the stellar evolution. Due to its complicated reaction mechanism, there is great uncertainty in the reaction rate which limits our understanding of various stellar objects, such as massive stellar evolution, explosions on neutron stars, and supernovae from accreting white dwarf stars. In this paper, I will review the challenges in the study of carbon burning. I will also report recent results from our studies: 1) an upper limit for the 12 C + 12 C fusion cross sections, 2) measurement of the 12 C + 12 C at deep sub-barrier energies, and 3) a new measurement of the 12 C( 12 C, n) reaction. The outlook for the studies of the astrophysical heavy-ion fusion reactions will also be presented

Bioconductor: open software development for computational biology and bioinformatics

DEFF Research Database (Denmark)

Gentleman, R.C.; Carey, V.J.; Bates, D.M.

2004-01-01

The Bioconductor project is an initiative for the collaborative creation of extensible software for computational biology and bioinformatics. The goals of the project include: fostering collaborative development and widespread use of innovative software, reducing barriers to entry into interdisci......The Bioconductor project is an initiative for the collaborative creation of extensible software for computational biology and bioinformatics. The goals of the project include: fostering collaborative development and widespread use of innovative software, reducing barriers to entry...... into interdisciplinary scientific research, and promoting the achievement of remote reproducibility of research results. We describe details of our aims and methods, identify current challenges, compare Bioconductor to other open bioinformatics projects, and provide working examples....

Deep inelastic collisions at near-barrier energies and search for cold donor-fragment production

International Nuclear Information System (INIS)

Chatterjee, M.B.

1992-01-01

Deep inelastic collisions in the near barrier energies of the mass asymmetric systems are of importance since controversial results on energy partition are being reported. Energy dissipation and the partition of dissipated energy among the reaction partners are of interest. Search for cold donor-fragment production at near barrier energies were carried out on a mass asymmetric system like Ni+Pb. (author). 13 refs., 8 figs

Comparison of classical reaction paths and tunneling paths studied with the semiclassical instanton theory.

Science.gov (United States)

Meisner, Jan; Markmeyer, Max N; Bohner, Matthias U; Kästner, Johannes

2017-08-30

Atom tunneling in the hydrogen atom transfer reaction of the 2,4,6-tri-tert-butylphenyl radical to 3,5-di-tert-butylneophyl, which has a short but strongly curved reaction path, was investigated using instanton theory. We found the tunneling path to deviate qualitatively from the classical intrinsic reaction coordinate, the steepest-descent path in mass-weighted Cartesian coordinates. To perform that comparison, we implemented a new variant of the predictor-corrector algorithm for the calculation of the intrinsic reaction coordinate. We used the reaction force analysis method as a means to decompose the reaction barrier into structural and electronic components. Due to the narrow energy barrier, atom tunneling is important in the abovementioned reaction, even above room temperature. Our calculated rate constants between 350 K and 100 K agree well with experimental values. We found a H/D kinetic isotope effect of almost 10 6 at 100 K. Tunneling dominates the protium transfer below 400 K and the deuterium transfer below 300 K. We compared the lengths of the tunneling path and the classical path for the hydrogen atom transfer in the reaction HCl + Cl and quantified the corner cutting in this reaction. At low temperature, the tunneling path is about 40% shorter than the classical path.

Biological permeable reactive barriers coupled with electrokinetic soil flushing for the treatment of diesel-polluted clay soil.

Science.gov (United States)

Mena, Esperanza; Ruiz, Clara; Villaseñor, José; Rodrigo, Manuel A; Cañizares, Pablo

2015-01-01

Removal of diesel from spiked kaolin has been studied in the laboratory using coupled electrokinetic soil flushing (EKSF) and bioremediation through an innovative biological permeable reactive barriers (Bio-PRBs) positioned between electrode wells. The results show that this technology is efficient in the removal of pollutants and allows the soil to maintain the appropriate conditions for microorganism growth in terms of pH, temperature, and nutrients. At the same time, EKSF was demonstrated to be a very interesting technology for transporting pollutants, microorganisms and nutrients, although results indicate that careful management is necessary to avoid the depletion of nutrients, which are effectively transported by electro-migration. After two weeks of operation, 30% of pollutants are removed and energy consumption is under 70 kWh m(-3). Main fluxes (electroosmosis and evaporation) and changes in the most relevant parameters (nutrients, diesel, microorganisms, surfactants, moisture conductivity and pH) during treatment and in a complete post-study analysis are studied to give a comprehensive description of the most relevant processes occurring in the soil (pollutant transport and biodegradation). Copyright © 2014 Elsevier B.V. All rights reserved.

Surface Cracking and Interface Reaction Associated Delamination Failure of Thermal and Environmental Barrier Coatings

National Research Council Canada - National Science Library

Zhu, Dongming

2003-01-01

...%Y2O3 and mullite/BSAS/Si thermal and environmental barrier coating system on SiC/SiC ceramic matrix composites were characterized after long-term combined laser thermal gradient and furnace cyclic...

Understanding barriers to glycaemic control from the patient's perspective

Directory of Open Access Journals (Sweden)

Janes R

2013-06-01

Full Text Available INTRODUCTION: To better understand barriers to glycaemic control from the patient's perspective. METHODS: An interpretative phenomenological approach was used to study the experiences of 15 adults with Type 2 diabetes. Participants each gave a semi-structured interview of their experiences of living with diabetes. Interviews were transcribed, and themes extracted and organised using a patientcentred framework. FINDINGS: Participants' stories confirmed many of the barriers in the literature, particularly those related to context, such as family, finances, work. Barriers also related to negative emotional reactions to diabetes: fear of new events (diagnosis, starting pills/insulin; guilt about getting diabetes and not controlling it; and shame about having diabetes. Barriers also related to unscientific beliefs and personal beliefs. There were additional barriers related to poor clinician-patient relationships. Overall, participants had a poor understanding of diabetes, and complained that their clinician simply 'told them what to do'. CONCLUSION: Using a patient-centred approach, this study identified many barriers to glycaemic control. We suggest that a key barrier is clinician ignorance of their patients' fears, beliefs, expectations, context; of what constitutes a positive therapeutic relationship; and of the limitations of a biomedical approach to patient non-adherence. Faced with both a worsening diabetes epidemic and increasing health care workforce shortages, clinicians urgently need to understand that it is they, not their patients, who must change their approach if diabetes care is to be improved.

Comments on the current status and possible future directions of research on heavy-ion interactions near the Coulomb barrier

International Nuclear Information System (INIS)

Satchler, G.R.

1990-01-01

This paper contains comments on the current status and possible future directions of research on heavy-ion interactions near the Coulomb barrier. Fusion reactions, elastic and inelastic scattering and transfer reactions are discussed

Biosensor Technology Reveals the Disruption of the Endothelial Barrier Function and the Subsequent Death of Blood Brain Barrier Endothelial Cells to Sodium Azide and Its Gaseous Products.

Science.gov (United States)

Kho, Dan T; Johnson, Rebecca H; O'Carroll, Simon J; Angel, Catherine E; Graham, E Scott

2017-09-21

Herein we demonstrate the sensitive nature of human blood-brain barrier (BBB) endothelial cells to sodium azide and its gaseous product. Sodium azide is known to be acutely cytotoxic at low millimolar concentrations, hence its use as a biological preservative (e.g., in antibodies). Loss of barrier integrity was noticed in experiments using Electric Cell-substrate Impedance Sensing (ECIS) biosensor technology, to measure endothelial barrier integrity continuously in real-time. Initially the effect of sodium azide was observed as an artefact where it was present in antibodies being employed in neutralisation experiments. This was confirmed where antibody clones that were azide-free did not mediate loss of barrier function. A delayed loss of barrier function in neighbouring wells implied the influence of a liberated gaseous product. ECIS technology demonstrated that the BBB endothelial cells had a lower level of direct sensitivity to sodium azide of ~3 µM. Evidence of gaseous toxicity was consistently observed at 30 µM and above, with disrupted barrier function and cell death in neighbouring wells. We highlight the ability of this cellular biosensor technology to reveal both the direct and gaseous toxicity mediated by sodium azide. The sensitivity and temporal dimension of ECIS technology was instrumental in these observations. These findings have substantial implications for the wide use of sodium azide in biological reagents, raising issues of their application in live-cell assays and with regard to the protection of the user. This research also has wider relevance highlighting the sensitivity of brain endothelial cells to a known mitochondrial disruptor. It is logical to hypothesise that BBB endothelial dysfunction due to mitochondrial dys-regulation could have an important but underappreciated role in a range of neurological diseases.

Fusion around the barrier for Li ·12 C

Indian Academy of Sciences (India)

Abstract. Fusion cross-sections for the Li +½¾. C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from thea-particles in the spectrum and hence their contribution was ...

Mechanisms and Barriers in Cancer Nanomedicine: Addressing Challenges, Looking for Solutions.

Science.gov (United States)

Anchordoquy, Thomas J; Barenholz, Yechezkel; Boraschi, Diana; Chorny, Michael; Decuzzi, Paolo; Dobrovolskaia, Marina A; Farhangrazi, Z Shadi; Farrell, Dorothy; Gabizon, Alberto; Ghandehari, Hamidreza; Godin, Biana; La-Beck, Ninh M; Ljubimova, Julia; Moghimi, S Moein; Pagliaro, Len; Park, Ji-Ho; Peer, Dan; Ruoslahti, Erkki; Serkova, Natalie J; Simberg, Dmitri

2017-01-24

Remarkable progress has recently been made in the synthesis and characterization of engineered nanoparticles for imaging and treatment of cancers, resulting in several promising candidates in clinical trials. Despite these advances, clinical applications of nanoparticle-based therapeutic/imaging agents remain limited by biological, immunological, and translational barriers. In order to overcome the existing status quo in drug delivery, there is a need for open and frank discussion in the nanomedicine community on what is needed to make qualitative leaps toward translation. In this Nano Focus, we present the main discussion topics and conclusions from a recent workshop: "Mechanisms and Barriers in Nanomedicine". The focus of this informal meeting was on biological, toxicological, immunological, and translational aspects of nanomedicine and approaches to move the field forward productively. We believe that these topics reflect the most important issues in cancer nanomedicine.

Direct Visualization of Barrier Crossing Dynamics in a Driven Optical Matter System.

Science.gov (United States)

Figliozzi, Patrick; Peterson, Curtis W; Rice, Stuart A; Scherer, Norbert F

2018-04-25

A major impediment to a more complete understanding of barrier crossing and other single-molecule processes is the inability to directly visualize the trajectories and dynamics of atoms and molecules in reactions. Rather, the kinetics are inferred from ensemble measurements or the position of a transducer ( e. g., an AFM cantilever) as a surrogate variable. Direct visualization is highly desirable. Here, we achieve the direct measurement of barrier crossing trajectories by using optical microscopy to observe position and orientation changes of pairs of Ag nanoparticles, i. e. passing events, in an optical ring trap. A two-step mechanism similar to a bimolecular exchange reaction or the Michaelis-Menten scheme is revealed by analysis that combines detailed knowledge of each trajectory, a statistically significant number of repetitions of the passing events, and the driving force dependence of the process. We find that while the total event rate increases with driving force, this increase is due to an increase in the rate of encounters. There is no drive force dependence on the rate of barrier crossing because the key motion for the process involves a random (thermal) radial fluctuation of one particle allowing the other to pass. This simple experiment can readily be extended to study more complex barrier crossing processes by replacing the spherical metal nanoparticles with anisotropic ones or by creating more intricate optical trapping potentials.

Innovations in Undergraduate Chemical Biology Education.

Science.gov (United States)

Van Dyke, Aaron R; Gatazka, Daniel H; Hanania, Mariah M

2018-01-19

Chemical biology derives intellectual vitality from its scientific interface: applying chemical strategies and perspectives to biological questions. There is a growing need for chemical biologists to synergistically integrate their research programs with their educational activities to become holistic teacher-scholars. This review examines how course-based undergraduate research experiences (CUREs) are an innovative method to achieve this integration. Because CUREs are course-based, the review first offers strategies for creating a student-centered learning environment, which can improve students' outcomes. Exemplars of CUREs in chemical biology are then presented and organized to illustrate the five defining characteristics of CUREs: significance, scientific practices, discovery, collaboration, and iteration. Finally, strategies to overcome common barriers in CUREs are considered as well as future innovations in chemical biology education.

Inverse problems in systems biology

International Nuclear Information System (INIS)

Engl, Heinz W; Lu, James; Müller, Stefan; Flamm, Christoph; Schuster, Peter; Kügler, Philipp

2009-01-01

Systems biology is a new discipline built upon the premise that an understanding of how cells and organisms carry out their functions cannot be gained by looking at cellular components in isolation. Instead, consideration of the interplay between the parts of systems is indispensable for analyzing, modeling, and predicting systems' behavior. Studying biological processes under this premise, systems biology combines experimental techniques and computational methods in order to construct predictive models. Both in building and utilizing models of biological systems, inverse problems arise at several occasions, for example, (i) when experimental time series and steady state data are used to construct biochemical reaction networks, (ii) when model parameters are identified that capture underlying mechanisms or (iii) when desired qualitative behavior such as bistability or limit cycle oscillations is engineered by proper choices of parameter combinations. In this paper we review principles of the modeling process in systems biology and illustrate the ill-posedness and regularization of parameter identification problems in that context. Furthermore, we discuss the methodology of qualitative inverse problems and demonstrate how sparsity enforcing regularization allows the determination of key reaction mechanisms underlying the qualitative behavior. (topical review)

The influence of transfer reactions on the sub-barrier fusion enhancement in the systems {sup 58.64}Ni +, {sup 92,100}Mo

Energy Technology Data Exchange (ETDEWEB)

Rehm, K.E.; Jiang, C.L.; Esbensen, H. [and others

1995-08-01

High resolution experiments performed during the past few years demonstrated that the various reaction modes occurring in heavy ion collisions can strongly influence each other. This interrelation of the different reaction modes brings a nuclear structure dependence to the fusion and deep-inelastic channels that were previously described in the framework of pure statistical models. In order to fully understand the interrelation between these reaction channels, a complete set of measurements including elastic and inelastic scattering, few-nucleon transfer and fusion is required. In continuation of our earlier measurements of the fusion cross sections in the system {sup 58,64}Ni + {sup 92,100}Mo we finished the studies of the quasielastic process in these systems. The experiments were done in inverse reaction kinematics using the split-pole spectrograph with its hybrid focal-plane detector for particle identification. The experiments with {sup 100}Mo beams were performed previously. First test runs with {sup 92}Mo showed the possible interference with {sup 98}Mo ions which could be eliminated by using the 13{sup +} charge state from the ECR source. The data from these experiments were completely analyzed. The smallest transfer cross sections are observed for the systems {sup 64}Ni + {sup 100}Mo and {sup 58}Ni + {sup 92}Mo, i.e., the most neutron-rich and neutron-deficient systems, respectively. For the other systems, {sup 64}Ni + {sup 92}Mo and {sup 58}Ni + {sup 100}Mo, the transfer cross sections at energies close to the barrier are about of equal magnitude. This observation does not correlate with the deviation of the experimental fusion cross sections from the coupled-channels predictions. While for {sup 58}Ni + {sup 100}Mo discrepancies between the experimental and theoretical fusion cross sections are observed, the system {sup 64}Ni + {sup 92}Mo which shows about the same transfer yields, is quite well described by the coupled-channels calculations.

Specific fission J-window and angular momentum dependence of the fission barrier

Energy Technology Data Exchange (ETDEWEB)

Baba, Hiroshi; Saito, Tadashi; Takahashi, Naruto; Yokoyama, Akihiko [Osaka Univ., Suita (Japan); Shinohara, Atsushi

1997-04-01

A method to determine a unique J-window in the fission process was devised and the fissioning nuclide associated with thus extracted J-window was identified for each of the heavy-ion reaction systems. Obtained fission barriers at the resulting J-window were compared with the calculated values by the rotating finite range model (RFRM). The deduced barriers for individual nuclides were compared with the RFRM barriers to reproduce more or less the angular momentum dependence the RFRM prediction. The deduced systematic behavior of the fission barrier indicates no even-odd and shell corrections are necessary. The nuclear dissipation effect based on Kramer`s model revealed substantial reduction of the statistically deduced barrier heights and brought a fairly large scattering from the RFRM J-dependence. However, introduction of the temperature-dependent friction coefficient ({gamma} = 2 for T {>=} 1.0 MeV and 0.5 for T < 1.0 MeV) was found to bring about satisfactory agreement with both RFRM fission barriers and the pre-fission neutron multiplicity systematics. (author). 81 refs.

Semi empirical model for astrophysical nuclear fusion reactions of 1≤Z≤15

International Nuclear Information System (INIS)

Manjunatha, H.C.; Seenappa, L.; Sridhar, K.N.

2017-01-01

The fusion reaction is one of the most important reactions in the stellar evolution. Due to the complicated reaction mechanism of fusion, there is great uncertainty in the reaction rate which limits our understanding of various stellar objects. Low z elements are formed through many fusion reactions such as "4He+"1"2C→"1"6O, "1"2C+"1"2C→"2"0Ne+"4He, "1"2C+"1"2C→"2"3Na, "1"2C+"1"2C→"2"3Mg, "1"6O+"1"6O→"2"8Si+"4He, "1"2C+"1H→"1"3N and "1"3C+"4He→"1"6O. A detail study is required on Coulomb and nuclear interaction in formation of low Z elements in stars through fusion reactions. For astrophysics, the important energy range extends from 1 MeV to 3 MeV in the center of mass frame, which is only partially covered by experiments. In the present work, we have studied the basic fusion parameters such as barrier heights (V_B), positions (R_B), curvature of the inverted parabola (ħω_1) for fusion barrier, cross section and compound nucleus formation probability (P_C_N) and fusion process in the low Z element (1≤Z≤15) formation process. For each isotope, we have studied all possible projectile-target combinations. We have also studied the astrophysical S(E) factor for these reactions. Based on this study, we have formulated the semi empirical relations for barrier heights (V_B), positions (R_B), curvature of the inverted parabola and hence for the fusion cross section and astrophysical S(E) factor. The values produced by the present model compared with the experiments and data available in the literature. (author)

Reflection at a complex potential barrier in the semiclassical theory of scattering

International Nuclear Information System (INIS)

Avishai, Y.; Knoll, J.

1976-01-01

The reflection of spherical waves at a complex potential barrier is discussed in the semiclassical approximation. We study the complex WKB method and the Uniform Approximation in the special case of weakly absorptive barriers, typical of surface transparent optical potentials used in heavy-ion reactions. It is found that the complex WKB results lead to a very accurate cross-section despite their inaccuracy in the most important phase shifts. Thereby, the amazing stamina of the WKB has been confirmed once more. (orig.) [de

Study on characteristics of high frequency dielectric barrier discharge for the removal of organic pollutant adsorbed on activated carbon

Energy Technology Data Exchange (ETDEWEB)

Qu, G.Z.; Li, G.F. [Dalian Univ. of Technology, Dalian (China). Inst. of Electrostatics and Special Power; Li, J.; Lu, N.; Wu, Y.; Li, D. [Dalian Univ. of Technology, Dalian (China). Inst. of Electrostatics and Special Power; Key Lab of Industrial Ecology and Environmental Engineering, Ministry of Education, Dalian (China)

2010-07-01

Advanced oxidation technologies such as photocatalysis, electrochemical degradation, Fenton oxidation, hydrogen peroxide oxidation, and plasma oxidation are increasingly being used to degrade refractory biodegradable organic contaminants. The plasma oxidation method has the advantage of direct in situ production of multiple types of high-reactive chemical species, including molecules and radicals that facilitate the degradation reaction. In addition, plasma oxidation does not produce any secondary pollution. Compared to other plasma technologies, the dielectric barrier discharge (DBD) plasma has been considered as a promising technology for removing toxic compounds because of its stability and its treatability property of biologically recalcitrant compounds in wastewater. However, the energy efficiency of DBD requires improvement for economic reasons. This paper reported on an experimental study that investigated the electrical characteristics of a parallel plate DBD reactor using a high frequency power supply for the removal of pentachlorophenol (PCP) adsorbed on activated carbon (AC). This study examined the effects of AC with different mass on discharge characteristics and compared the voltage and current waveforms, and discharge images of DBD reactors with different dielectric configurations. When the DBD reactor filled with AC, the applied voltage of discharge decreased regardless of the DBD reactor configuration in terms of having a single barrier or two barriers. The discharge characteristics had no significant change with AC mass increasing. The discharge images and current waveforms showed that DBD reactor configuration consisting of two dielectrics is more homogeneous and stable than the one consisting of a single dielectric. Under the same electric field condition, the degradation efficiency of PCP in two barriers reactor is higher than that in single barrier reactor. It was concluded that the findings from this study may be instrumental in treating

Reaction of LiD with moisture by temperature programmed reaction (TPR)

International Nuclear Information System (INIS)

Dinh, L N; Balooch, M; Cecala, C M; Leckey, J H

2000-01-01

The temperature programmed reaction technique was performed on LiOH powders and LiD single crystals previously exposed to different moisture levels. Our results show that the LiOH decomposition process has an activation energy barrier of 30 to 33.1 kcal/mol. The LiOH structure is stable at 320 K for 100 years. However, LiOH structures formed on the surface of LiD during moisture exposure at low dosages may have multiple activation energy barriers, some of which may be much lower than 30 kcal/mol. We attribute the lowering of the activation energy barrier for the LiOH decomposition to the existence of dangling bonds, cracks, and other long range disorders in the LiOH structures formed at low levels of moisture exposure. These defective LiOH structures may decompose significantly over the next 100 years of storage even at room temperature. At high moisture exposure levels, LiOH.H 2 O formation is observed. The release of H 2 O molecules from LiOH.H 2 O structure has small activation energy barriers in the range of 13.8 kcal/mol to 16.0 kcal/mol. The loosely bonded H 2 O molecules in the LiOH.H 2 O structure can be easily pumped away at room temperature in a reasonable amount of time. Our experiments also suggest that handling LiD single crystals at an elevated temperature of 340 K or more reduces the growth of LiOH and LiOH.H 2 O significantly

Determination of the fission barrier height in fission of heavy radioactive beams induced by the (d,p)-transfer

CERN Multimedia

A theoretical framework is described, allowing to determine the fission barrier height using the observed cross sections of fission induced by the (d,p)-transfer with accuracy, which is not achievable in another type of low-energy fission of neutron-deficient nuclei, the $\\beta$-delayed fission. The primary goal is to directly determine the fission barrier height of proton-rich fissile nuclei, preferably using the radio-active beams of isotopes of odd elements, and thus confirm or exclude the low values of fission barrier heights, typically extracted using statistical calculations in the compound nucleus reactions at higher excitation energies. Calculated fission cross sections in transfer reactions of the radioactive beams show sufficient sensitivity to fission barrier height. In the probable case that fission rates will be high enough, mass asymmetry of fission fragments can be determined. Results will be relevant for nuclear astrophysics and for production of super-heavy nuclei. Transfer induced fission of...

Biological hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Benemann, J.R. [Univ. of California, Berkeley, CA (United States)

1995-11-01

Biological hydrogen production can be accomplished by either thermochemical (gasification) conversion of woody biomass and agricultural residues or by microbiological processes that yield hydrogen gas from organic wastes or water. Biomass gasification is a well established technology; however, the synthesis gas produced, a mixture of CO and H{sub 2}, requires a shift reaction to convert the CO to H{sub 2}. Microbiological processes can carry out this reaction more efficiently than conventional catalysts, and may be more appropriate for the relatively small-scale of biomass gasification processes. Development of a microbial shift reaction may be a near-term practical application of microbial hydrogen production.

Isolation barriers between petunia axillaris and Petunia integrifolia (Solanaceae).

Science.gov (United States)

Dell'olivo, Alexandre; Hoballah, Maria Elena; Gübitz, Thomas; Kuhlemeier, Cris

2011-07-01

The isolation barriers restricting gene flow between populations or species are of crucial interest for understanding how biological species arise and how they are maintained. Few studies have examined the entire range of possible isolation barriers from geographic isolation to next generation hybrid viability. Here, we present a detailed analysis of isolation barriers between two flowering plant species of the genus Petunia (Solanaceae). Petunia integrifolia and P. axillaris feature divergent pollination syndromes but can produce fertile hybrids when crossed in the laboratory. Both Petunia species are primarily isolated in space but appear not to hybridize in sympatry. Our experiments demonstrate that pollinator isolation is very high but not strong enough to explain the absence of hybrids in nature. However, pollinator isolation in conjunction with male gametic isolation (i.e., pollen-pistil interaction) can explain the lack of natural hybridization, while postzygotic isolation barriers are low or nonexistent. Our study supports the notion that reproductive isolation in flowering plants is mainly caused by pre- rather than postzygotic isolation mechanisms. © 2011 The Author(s). Evolution© 2011 The Society for the Study of Evolution.

Classical kinematic model for direct reactions of oriented reagents

International Nuclear Information System (INIS)

Schechter, I.; Prisant, M.G.; Levine, R.D.

1987-01-01

A simple kinematic model based on the concept of an orientation-dependent critical configuration for reaction is introduced and applied. The model serves two complementary purposes. In the predictive mode the model provides an easily implemented procedure for computing the reactivity of oriented reagents (including those actually amenable to measure) from a given potential energy surface. The predictions of the model are compared against classical trajectory results for the H + D 2 reaction. By use of realistic potential energy surfaces the model is applied to the Li + HF and O + HCl reactions where the HX molecules are pumped by a polarized laser. A given classical trajectory is deemed reactive or not according to whether it can surmount the barrier at that particular orientation. The essential difference with the model of Levine and Bernstein is that the averaging over initial conditions is performed by using a Monte Carlo integration. One can therefore use the correct orientation-dependent shape (and not only height) of the barrier to reaction and, furthermore, use oriented or aligned reagents. Since the only numerical step is a Monte Carlo sampling of initial conditions, very many trajectories can be run. This suffices to determine the reaction cross section for different initial conditions. To probe the products, they have employed the kinematic approach of Elsum and Gordon. The result is a model where, under varying initial conditions, examining final-state distributions or screening different potential energy surfaces can be efficiently carried out

Chloridrate of N-isopropyl-p-iodoamphetamine labeled with Iodine-131. Biological distribution in laboratory animals

International Nuclear Information System (INIS)

Colturato, Maria Tereza; Muramoto, Emiko; Carvalho, Olga Goncalves de

2000-01-01

The development of this work was based on a great interest from the medical class in the utilization of chloridrate of N-isopropyl-p-iodoamphetamine (IMP) labeled with 123 I, for brain perfusion evaluation. Studies were performed to optimize the labeling parameters of IMP with 131 I using nucleophilic substitution: temperature and, time reaction, ascorbic acid mass, pH and relation IMP mass/radioiodo activity, and stability of the final product. Radiochemistry purity method used showed to be efficient, quick and of easily handling for routine production. Biological distribution studies were performed in mice to determine the percent administered dose in the blood, different organs and whole body after intravenous administration of the radiopharmaceutical. The product crossed the intact blood brain barrier, allowing a follow up of further studies after the intravenous administration of the radiopharmaceutical. The principal elimination route 131 I-IMP was the urinary. Based on the results from radiochemical purity, stability and biological behavior in laboratory animals, we concluded that the studied radiopharmaceutical presents all ideal characteristics for clinical use in brain studies in nuclear medicine. (author)

Exploring Reaction Mechanism on Generalized Force Modified Potential Energy Surfaces (G-FMPES) for Diels-Alder Reaction

Science.gov (United States)

Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

Selected aspects of fusion reactions

International Nuclear Information System (INIS)

Lacroix, D.

2003-01-01

In this lecture, we present selected aspects of nuclear fusion. The importance of the initial geometry of the reaction and its relation to fusion barrier are first discussed. The effect of deformation leading to the notion of barrier distribution is then illustrated. After a brief overview of the advantages of macroscopic theories, the dynamics of nuclear system under large amplitude motion is reviewed. The di-nuclear concept is presented to understand the competition between fusion and quasi-fission. This concept is then generalized to account for the dissipative dynamics in multidimensional collective space. The last part of this lecture is devoted to new aspects encountered with radioactive beams specific properties of very extended neutron rich system, influence of pygmy or soft dipole resonances and charge exchange far from stability are discussed. (author)

How does the carbon fusion reaction happen in stars?

Directory of Open Access Journals (Sweden)

X. Tang

2013-09-01

Full Text Available The 12C + 12C fusion reaction is one of the most important reactions in the stellar evolution. Due to its compli-cated reaction mechanism, there is great uncertainty in the reaction rate which limits our understanding of vari-ous stellar objects, such as explosions on the surface of neutron stars, white dwarf (type Ia supernovae, and massive stellar evolution. In this paper, I will review the challenges in the study of carbon burning. I will also report recent re-sults from our studies: 1 an upper limit for the 12C + 12C fusion cross sections, 2 measurement of the 12C + 12C at deep sub-barrier energies, 3 a new measurement of the 12C(12C, n reaction. The outlook for the studies of the astrophysical heavy-ion fusion reactions will also be presented.

Biological fuel cells and their applications

OpenAIRE

Shukla, AK; Suresh, P; Berchmans, S; Rajendran, A

2004-01-01

One type of genuine fuel cell that does hold promise in the long-term is the biological fuel cell. Unlike conventional fuel cells, which employ hydrogen, ethanol and methanol as fuel, biological fuel cells use organic products produced by metabolic processes or use organic electron donors utilized in the growth processes as fuels for current generation. A distinctive feature of biological fuel cells is that the electrode reactions are controlled by biocatalysts, i.e. the biological redox-reac...

Systems Biology of Metabolism: Annual Review of Biochemistry

DEFF Research Database (Denmark)

Nielsen, Jens

2017-01-01

Metabolism is highly complex and involves thousands of different connected reactions; it is therefore necessary to use mathematical models for holistic studies. The use of mathematical models in biology is referred to as systems biology. In this review, the principles of systems biology are descr...

Investigation of the CH3Cl + CN(-) reaction in water: Multilevel quantum mechanics/molecular mechanics study.

Science.gov (United States)

Xu, Yulong; Zhang, Jingxue; Wang, Dunyou

2015-06-28

The CH3Cl + CN(-) reaction in water was studied using a multilevel quantum mechanics/molecular mechanics (MM) method with the multilevels, electrostatic potential, density functional theory (DFT) and coupled-cluster single double triple (CCSD(T)), for the solute region. The detailed, back-side attack SN2 reaction mechanism was mapped along the reaction pathway. The potentials of mean force were calculated under both the DFT and CCSD(T) levels for the reaction region. The CCSD(T)/MM level of theory presents a free energy activation barrier height at 20.3 kcal/mol, which agrees very well with the experiment value at 21.6 kcal/mol. The results show that the aqueous solution has a dominant role in shaping the potential of mean force. The solvation effect and the polarization effect together increase the activation barrier height by ∼11.4 kcal/mol: the solvation effect plays a major role by providing about 75% of the contribution, while polarization effect only contributes 25% to the activation barrier height. Our calculated potential of mean force under the CCSD(T)/MM also has a good agreement with the one estimated using data from previous gas-phase studies.

Effects of electrode geometry on the performance of dielectric barrier/packed-bed discharge plasmas in benzene degradation

International Nuclear Information System (INIS)

Jiang, Nan; Lu, Na; Shang, Kefeng; Li, Jie; Wu, Yan

2013-01-01

Highlights: • Benzene was successfully degraded by dielectric barrier/packed-bed discharge plasmas. • Different electrode geometry has distinct effect on plasmas oxidation performance. • Benzene degradation and energy performance were enhanced when using the coil electrode. • The reaction products were well determined by online FTIR analysis. -- Abstract: In this study, the effects of electrode geometry on benzene degradation in a dielectric barrier/packed-bed discharge plasma reactor with different electrodes were systematically investigated. Three electrodes were employed in the experiments, these were coil, bolt, and rod geometries. The reactor using the coil electrode showed better performance in reducing the dielectric loss in the barrier compared to that using the bolt or rod electrodes. In the case of the coil electrode, both the benzene degradation efficiency and energy yield were higher than those for the other electrodes, which can be attributed to the increased role of surface mediated reactions. Irrespective of the electrode geometry, the packed-bed discharge plasma was superior to the dielectric barrier discharge plasma in benzene degradation at any specific applied voltage. The main gaseous products of benzene degradation were CO, CO 2 , H 2 O, and formic acid. Discharge products such as O 3 , N 2 O, N 2 O 5 , and HNO 3 were also detected in the outlet gas. Moreover, the presence of benzene inhibited the formation of ozone because of the competing reaction of oxygen atoms with benzene. This study is expected to offer an optimized approach combining dielectric barrier discharge and packed-bed discharge to improve the degradation of gaseous pollutants

Elastic scattering and fusion studies in the reactions $^{10,11}$Be + $^{64}$Zn

CERN Multimedia

2002-01-01

We propose to measure elastic scattering and fusion excitation functions for the reactions $^{10,11}$Be + $^{64}$Zn at 3.1 MeV/u . The aim of the experiment is to investigate possible effects of the halo structure of the $^{11}$Be nucleus on the reaction mechanisms at energy around the Coulomb barrier. For this purpose a comparison with the reaction induced by the $^{10}$Be nucleus is required.

Inertial effects in diffusion-limited reactions

International Nuclear Information System (INIS)

Dorsaz, N; Foffi, G; De Michele, C; Piazza, F

2010-01-01

Diffusion-limited reactions are commonly found in biochemical processes such as enzyme catalysis, colloid and protein aggregation and binding between different macromolecules in cells. Usually, such reactions are modeled within the Smoluchowski framework by considering purely diffusive boundary problems. However, inertial effects are not always negligible in real biological or physical media on typical observation time frames. This is all the more so for non-bulk phenomena involving physical boundaries, that introduce additional time and space constraints. In this paper, we present and test a novel numerical scheme, based on event-driven Brownian dynamics, that allows us to explore a wide range of velocity relaxation times, from the purely diffusive case to the underdamped regime. We show that our algorithm perfectly reproduces the solution of the Fokker-Planck problem with absorbing boundary conditions in all the regimes considered and is thus a good tool for studying diffusion-guided reactions in complex biological environments.

Microscopic approach of molecular dynamics. Applications to reactions near the barrier; Approches microscopiques de la dynamique nucleaire. Applications aux reactions autour de la barriere

Energy Technology Data Exchange (ETDEWEB)

Simenel, C.; Avez, B. [CEA Saclay, Dept. d' Astrophysique, de Physique des Particules de Physique Nucleaire et de l' Instrumentation Associee (DSM/DAPNIA/SPhN), 91- Gif sur Yvette (France); Lacroix, D. [GANIL, 14 - Caen (France)

2007-07-01

This lecture introduces several microscopic approaches to nuclear dynamics. Our goal is to provide a good description of low energy heavy ions collisions. We study both the formalism and the practical application of the time-dependent Hartree-Fock (TDHF) theory. The TDHF approach gives a mean field dynamics of the system under the assumption of independent particles. As an example, we study the fusion of both spherical and deformed nuclei with TDHF. We also show that nucleon transfer may occur between nuclei below the barrier. These studies allow us to specify the field of applications of TDHF in one hand, and, in the other hand, its intrinsic limitations, as for instance the fact that there is no fusion by tunnel effect with TDHF. It is then important to get rid of the independent particle assumption. We finally present some approaches to go beyond TDHF, including for instance pairing and/or collision term between nucleons, though only few realistic applications have been performed so far. (authors)

A construção social de gênero na Biologia: preconceitos e obstáculos na biologia molecular Social construction of gender in biology: prejudice and barriers in molecular biology

Directory of Open Access Journals (Sweden)

Neide Mayumi Osada

2006-12-01

Full Text Available Este paper tem como objetivo analisar a presença de homens e mulheres nas ciências biológicas a partir do Projeto Genoma Fapesp (PGF. Baseado nos estudos sociais das ciências e nos estudos de gênero em ciências, pretende-se, portanto, entender as principais razões que levam ao avanço mais lento na carreira das mulheres pesquisadoras, analisar como ocorre a participação das mulheres na construção das ciências e, por fim, avaliar os principais obstáculos por elas enfrentados.This paper analyses the presence of women and men in Biological Sciences, specifically at the Fapesp Genome Project. Considering the Social Studies of Sciences and Gender Studies, this article highlights the barrier and prejudices women face in their scientific carrier and show how this reproduces a situation in which men advance faster than women.

The biofiltration permeable reactive barrier: Practical experience from Synthesia

Energy Technology Data Exchange (ETDEWEB)

Vesela, L.; Nemecek, J.; Siglova, M.; Kubal, M. [DEKONTA, Prague (Czech Republic)

2006-10-15

The paper refers to utilization of biological elements within permeable reactive barriers. The concept of a biofiltration permeable barrier has been tested in the laboratory and in pilot-scale. Oxyhumolite (oxidized young lignite) was examined as an absorption material and a biofilm carrier. Laboratory tests performed before the pilot verification confirmed that oxyhumolite adsorbs organic pollutants at a minimum value, but that it can be used for biofilm attachment. An experimental barrier was built on premises of a chemical factory contaminated mainly by various organic pollutants (benzene, toluene, ethylbenzene, and xylenes (BTEX), chlorobenzenes, naphthalene, nitro-derivatives, phenols, trichloroethylene (TCE), and total petroleum hydrocarbon (TPH)). Before the barrier was installed, a preliminary survey of the unsaturated zone, hydrogeological investigation, and a microbiological survey had been performed. The barrier was designed as a trench-and-gate system with an in situ bioreactor. During the year 2004, measurements of groundwater flux and retention time under current hydrological conditions, together with chemical and microbiological monitoring, were carried out on the site. The results showed high effectiveness of organic contamination removal. Average elimination varied from 57.3% (naphthalene) to 99.9% (nitro-derivatives, BTEX); microbial density in the bioreactor was approx. 10{sup 5} CFU mL{sup -1}.

Chemical dynamics simulations of X- + CH3Y → XCH3 + Y- gas-phase S(N)2 nucleophilic substitution reactions. Nonstatistical dynamics and nontraditional reaction mechanisms.

Science.gov (United States)

Manikandan, Paranjothy; Zhang, Jiaxu; Hase, William L

2012-03-29

Extensive classical chemical dynamics simulations of gas-phase X(-) + CH(3)Y → XCH(3) + Y(-) S(N)2 nucleophilic substitution reactions are reviewed and discussed and compared with experimental measurements and predictions of theoretical models. The primary emphasis is on reactions for which X and Y are halogen atoms. Both reactions with the traditional potential energy surface (PES), which include pre- and postreaction potential energy minima and a central barrier, and reactions with nontraditional PESs are considered. These S(N)2 reactions exhibit important nonstatistical atomic-level dynamics. The X(-) + CH(3)Y → X(-)---CH(3)Y association rate constant is less than the capture model as a result of inefficient energy transfer from X(-)+ CH(3)Y relative translation to CH(3)Y rotation and vibration. There is weak coupling between the low-frequency intermolecular modes of the X(-)---CH(3)Y complex and higher frequency CH(3)Y intramolecular modes, resulting in non-RRKM kinetics for X(-)---CH(3)Y unimolecular decomposition. Recrossings of the [X--CH(3)--Y](-) central barrier is important. As a result of the above dynamics, the relative translational energy and temperature dependencies of the S(N)2 rate constants are not accurately given by statistical theory. The nonstatistical dynamics results in nonstatistical partitioning of the available energy to XCH(3) +Y(-) reaction products. Besides the indirect, complex forming atomic-level mechanism for the S(N)2 reaction, direct mechanisms promoted by X(-) + CH(3)Y relative translational or CH(3)Y vibrational excitation are possible, e.g., the roundabout mechanism.

Computational structural biology: methods and applications

National Research Council Canada - National Science Library

Schwede, Torsten; Peitsch, Manuel Claude

2008-01-01

... sequencing reinforced the observation that structural information is needed to understand the detailed function and mechanism of biological molecules such as enzyme reactions and molecular recognition events. Furthermore, structures are obviously key to the design of molecules with new or improved functions. In this context, computational structural biology...

Aligning Metabolic Pathways Exploiting Binary Relation of Reactions.

Directory of Open Access Journals (Sweden)

Yiran Huang

Full Text Available Metabolic pathway alignment has been widely used to find one-to-one and/or one-to-many reaction mappings to identify the alternative pathways that have similar functions through different sets of reactions, which has important applications in reconstructing phylogeny and understanding metabolic functions. The existing alignment methods exhaustively search reaction sets, which may become infeasible for large pathways. To address this problem, we present an effective alignment method for accurately extracting reaction mappings between two metabolic pathways. We show that connected relation between reactions can be formalized as binary relation of reactions in metabolic pathways, and the multiplications of zero-one matrices for binary relations of reactions can be accomplished in finite steps. By utilizing the multiplications of zero-one matrices for binary relation of reactions, we efficiently obtain reaction sets in a small number of steps without exhaustive search, and accurately uncover biologically relevant reaction mappings. Furthermore, we introduce a measure of topological similarity of nodes (reactions by comparing the structural similarity of the k-neighborhood subgraphs of the nodes in aligning metabolic pathways. We employ this similarity metric to improve the accuracy of the alignments. The experimental results on the KEGG database show that when compared with other state-of-the-art methods, in most cases, our method obtains better performance in the node correctness and edge correctness, and the number of the edges of the largest common connected subgraph for one-to-one reaction mappings, and the number of correct one-to-many reaction mappings. Our method is scalable in finding more reaction mappings with better biological relevance in large metabolic pathways.

Tunneling in the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H reaction and its isotopic analog: an anomalous isotope effect

Energy Technology Data Exchange (ETDEWEB)

Kurosaki, Yuzuru; Takayanagi, Toshiyuki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1998-10-01

Vibrationally adiabatic ground-state potential curves for the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H (I) and CD{sub 3} + H{sub 2} {yields} CD{sub 4}H + H (II) reactions were obtained by adding zero-point energies of harmonic vibrations orthogonal to intrinsic reaction coordinate (IRC) to bare potential curves along IRC. It was clarified that both the barrier height and barrier width of reaction II are smaller than those of reaction I. This computational result qualitatively explains the experimental observation of Momose et al. (J. Chem. Phys. 108 (1998) 7334) that reaction II occurs but reaction I does not occur in solid parahydrogen at 5 K. (author)

Optimal systematics of single-humped fission barriers for statistical calculations

International Nuclear Information System (INIS)

Mashnik, S.G.

1993-01-01

A systematic comparison of the existing phenomenological approaches and models for describing single-humped fast-computing fission barriers are given. The experimental data on excitation energy dependence of the fissility of compound nuclei are analyzed in the framework of the statistical approach by using different models for fission barriers, shell and pairing corrections and level-density parameter in order to identify their reliability and region of applicability for Monte Carlo calculations of evaporative cascades. The energy dependence of fission cross-sections for reactions induced by intermediate energy protons has been analyzed in the framework of the cascade-exiton model. 53 refs., 15 figs., 3 tabs

Barrier Coatings for Refractory Metals and Superalloys

Energy Technology Data Exchange (ETDEWEB)

SM Sabol; BT Randall; JD Edington; CJ Larkin; BJ Close

2006-02-23

In the closed working fluid loop of the proposed Prometheus space nuclear power plant (SNPP), there is the potential for reaction of core and plant structural materials with gas phase impurities and gas phase transport of interstitial elements between superalloy and refractory metal alloy components during service. Primary concerns are surface oxidation, interstitial embrittlement of refractory metals and decarburization of superalloys. In parallel with kinetic investigations, this letter evaluates the ability of potential coatings to prevent or impede communication between reactor and plant components. Key coating requirements are identified and current technology coating materials are reviewed relative to these requirements. Candidate coatings are identified for future evaluation based on current knowledge of design parameters and anticipated environment. Coatings were identified for superalloys and refractory metals to provide diffusion barriers to interstitial transport and act as reactive barriers to potential oxidation. Due to their high stability at low oxygen potential, alumina formers are most promising for oxidation protection given the anticipated coolant gas chemistry. A sublayer of iridium is recommended to provide inherent diffusion resistance to interstitials. Based on specific base metal selection, a thin film substrate--coating interdiffusion barrier layer may be necessary to meet mission life.

Barrier Coatings for Refractory Metals and Superalloys

International Nuclear Information System (INIS)

SM Sabol; BT Randall; JD Edington; CJ Larkin; BJ Close

2006-01-01

In the closed working fluid loop of the proposed Prometheus space nuclear power plant (SNPP), there is the potential for reaction of core and plant structural materials with gas phase impurities and gas phase transport of interstitial elements between superalloy and refractory metal alloy components during service. Primary concerns are surface oxidation, interstitial embrittlement of refractory metals and decarburization of superalloys. In parallel with kinetic investigations, this letter evaluates the ability of potential coatings to prevent or impede communication between reactor and plant components. Key coating requirements are identified and current technology coating materials are reviewed relative to these requirements. Candidate coatings are identified for future evaluation based on current knowledge of design parameters and anticipated environment. Coatings were identified for superalloys and refractory metals to provide diffusion barriers to interstitial transport and act as reactive barriers to potential oxidation. Due to their high stability at low oxygen potential, alumina formers are most promising for oxidation protection given the anticipated coolant gas chemistry. A sublayer of iridium is recommended to provide inherent diffusion resistance to interstitials. Based on specific base metal selection, a thin film substrate--coating interdiffusion barrier layer may be necessary to meet mission life

Aspartate aminotransferase: the kinetic barriers facing the covalent intermediates on the reaction pathway

International Nuclear Information System (INIS)

Kirsch, J.F.; Julin, D.A.; McLeish, M.; Wiesinger, H.

1986-01-01

The intermediates, aldimine (A), quinonoid (Q) and ketimine (K), along the transaminase reaction coordinate were probed by isotope transfer and solvent exchange kinetics. Less than 0.003% of 3 H is transferred from C/sub α/[ 3 H]-aspartate to pyridoxamine phosphate in the cytoplasmic aspartate aminotransferase (cAATase) reaction implying either that Q does not exist as a kinetically competent intermediate or that there is a rapid exchange of isotope with solvent. The ratio of the rate constants for C/sub α/ hydrogen exchange vs keto acid product formation (k/sub exge//k/sub prod/) are 2.5 and 0.5 for the reactions of cAATase with C/sub α/ [ 2 H]-aspartate and mitochondrial (m) AATase with C/sub α/[ 2 H]-glutamate respectively. The latter reaction was also probed from the α-keto-glutarate side with carbonyl 0-18 enriched keto acid. This experiment gave k/sub exge//k/sub prod/ = 1.0 for oxygen-18 exchange in α-ketoglutarate versus amino acid formation. The two exchange experiments with mAATase are interpreted in terms of a model in which the rate constant for diffusion of water from the active site is comparable with those for product forming steps

The barrier to ice nucleation in monatomic water

Science.gov (United States)

Prestipino, Santi

2018-03-01

Crystallization from a supercooled liquid initially proceeds via the formation of a small solid embryo (nucleus), which requires surmounting an activation barrier. This phenomenon is most easily studied by numerical simulation, using specialized biased-sampling techniques to overcome the limitations imposed by the rarity of nucleation events. Here, I focus on the barrier to homogeneous ice nucleation in supercooled water, as represented by the monatomic-water model, which in the bulk exhibits a complex interplay between different ice structures. I consider various protocols to identify solidlike particles on a computer, which perform well enough for the Lennard-Jones model, and compare their respective impact on the shape and height of the nucleation barrier. It turns out that the effect is stronger on the nucleus size than on the barrier height. As a by-product of the analysis, I determine the structure of the nucleation cluster, finding that the relative amount of ice phases in the cluster heavily depends on the method used for classifying solidlike particles. Moreover, the phase which is most favored during the earlier stages of crystallization may happen, depending on the nucleation coordinate adopted, to be different from the stable polymorph. Therefore, the quality of a reaction coordinate cannot be assessed simply on the basis of the barrier height obtained. I explain how this outcome is possible and why it just points out the shortcoming of collective variables appropriate to simple fluids in providing a robust method of particle classification for monatomic water.

Sprache als Barriere (Language as a Barrier)

Science.gov (United States)

Mattheier, Klaus

1974-01-01

The concept of language barrier has its derivations in the fields of dialectology, sociology and psychology. In contemporary usage however, the concept has two meanings i.e. regional-cultural barrier and socio-cultural barrier. (Text is in German.) (DS)

Transfer reactions in sup(32,36)S + sup(144,154)Sm

International Nuclear Information System (INIS)

Pacheco, A.J.; Tada, M. di; Fernandez Niello, J.; Testoni, J.E.

1990-01-01

The deformation of spherical nuclei in transfer reactions near to the coulomb barrier is studied. The sup(32,36)S + sup(144,154)Sm reactions were carried out using sup(32)S beams produced by TANDAR accelerator in Buenos Aires with energies of 148 MeV and 160 MeV and sup(36)S beams produced by tandem accelerator of Laboratorio Nazionale di Legnaro with energies of 142 MeV and 155 MeV. The angular distributions were measured for sup(32)S reaction using gas ionization chamber and position sensitive detector. The mass spectra of reaction products were obtained measuring time of flight between time detectors, in the sup(36)S reaction. (M.C.K.)

Concurrent bioremediation of perchlorate and 1,1,1-trichloroethane in an emulsified oil barrier

Science.gov (United States)

Borden, Robert C.

2007-10-01

A detailed field pilot test was conducted to evaluate the use of edible oil emulsions for enhanced in situ biodegradation of perchlorate and chlorinated solvents in groundwater. Edible oil substrate (EOS®) was injected into a line of ten direct push injection wells over a 2-day period to form a 15-m-long biologically active permeable reactive barrier (bio-barrier). Field monitoring results over a 2.5-year period indicate the oil injection generated strongly reducing conditions in the oil-treated zone with depletion of dissolved oxygen, nitrate, and sulfate, and increases in dissolved iron, manganese and methane. Perchlorate was degraded from 3100 to 20,000 μg/L to below detection (oil and adaptation of the in situ microbial community. Approximately 4 months after emulsion injection, concentrations of 1,1,1-trichloroethane (TCA), perchloroethene (PCE), trichloroethene (TCE) and their degradation products appeared to reach a quasi steady-state condition. During the period from 4 to 18 months, TCA was reduced from 30-70 μM to 0.2-4 μM during passage through the bio-barrier. However, 1-9 μM 1,1-dichloroethane (DCA) and 8-14 μM of chloroethane (CA) remained indicating significant amounts of incompletely degraded TCA were discharging from the oil-treated zone. During this same period, PCE and TCE were reduced with concurrent production of 1,2- cis-dichloroethene ( cis-DCE). However, very little VC or ethene was produced indicating reductive dechlorination slowed or stopped at cis-DCE. The incomplete removal of TCA, PCE and TCE is likely associated with the short (5-20 days) hydraulic retention time of contaminants in the oil-treated zone. The permeability of the injection wells declined by 39-91% (average = 68%) presumably due to biomass growth and/or gas production. However, non-reactive tracer tests and detailed monitoring of the perchlorate plume demonstrated that the permeability loss did not result in excessive flow bypassing around the bio-barrier

Examining empirical evidence of the effect of superfluidity on the fusion barrier

Science.gov (United States)

Scamps, Guillaume

2018-04-01

Background: Recent time-dependent Hartree-Fock-Bogoliubov (TDHFB) calculations predict that superfluidity enhances fluctuations of the fusion barrier. This effect is not fully understood and not yet experimentally revealed. Purpose: The goal of this study is to empirically investigate the effect of superfluidity on the distribution width of the fusion barrier. Method: Two new methods are proposed in the present study. First, the local regression method is introduced and used to determine the barrier distribution. The second method, which requires only the calculation of an integral of the cross section, is developed to determine accurately the fluctuations of the barrier. This integral method, showing the best performance, is systematically applied to 115 fusion reactions. Results: Fluctuations of the barrier for open-shell systems are, on average, larger than those for magic or semimagic nuclei. This is due to the deformation and the superfluidity. To disentangle these two effects, a comparison is made between the experimental width and the width estimated from a model that takes into account the tunneling, the deformation, and the vibration effect. This study reveals that superfluidity enhances the fusion barrier width. Conclusions: This analysis shows that the predicted effect of superfluidity on the width of the barrier is real and is of the order of 1 MeV.

Barrier function test: Laboratory evaluation of the protective function of some barrier creams against cashewnut shell oil

Directory of Open Access Journals (Sweden)

Pasricha J

1991-01-01

Full Text Available A barrier function test has been designed to screen the protective capacity of a cream against the cauterizing effect of cashew nut shell oil (CNSO on the skin. The test consists of applying the barrier cream on a 5 cm circular area of skin on the back of a human volunteer and then at its centre applying a 1 cm sq Whatman no. 3 paper disc soaked in the CNSO for 15 minutes and looking for the evidence of cauterization reaction after 48 hours. Of the various creams containing a variety of paraffins, bees wax, polyethylene glycols, methyl cellulose gel, and petrolatum, only polyethylene glycol (PEG cream was found to afford adequate protection against cashew nut shell oil. Addition of 10% zinc oxide or 10% kaolin to the PEG cream did not seem to afford any additional protection. Castor oil already being used by the workers was found to be inferior to the PEG cream.

Stakeholders identify similar barriers but different strategies to facilitate return-to-work: A vignette of a worker with an upper extremity condition.

Science.gov (United States)

Peters, Susan E; Truong, Anthony P; Johnston, Venerina

2018-01-01

Stakeholders involved in the return-to-work (RTW) process have different roles and qualificationsOBJECTIVE:To explore the perspectives of Australian stakeholders of the RTW barriers and strategies for a worker with an upper extremity condition and a complex workers' compensation case. Using a case vignette, stakeholders were asked to identify barriers and recommend strategies to facilitate RTW. Content analysis was performed on the open-ended responses. The responses were categorised into RTW barriers and strategies using the biopsychosocial model. Pearson's Chi Square and ANOVA were performed to establish group differences. 621 participants (488 healthcare providers (HCPs), 62 employers, 55 insurers and 16 lawyers) identified 36 barriers (31 modifiable): 4 demographic; 8 biological; 15 psychological and 9 social barriers. 484 participants reported 16 RTW strategies: 4 biological; 6 psychological and 6 social strategies. 'Work relationship stressors' (83.4%) and 'Personal relationship stressors' (64.7%) were the most frequently nominated barriers. HCPs most frequently nominated 'Pain management' (49.6%), while employers, insurers and lawyers nominated 'RTW planning/Suitable duties programs' (40.5%; 42.9%; 80%). Stakeholders perceived similar barriers for RTW but recommended different strategies. Stakeholders appeared to be more proficient in identifying barriers than recommending strategies. Future research should focus on tools to both identify RTW barriers and direct intervention.

Study of fission barriers in neutron-rich nuclei using the (p,2p) reaction. Status of SAMURAI-experiment NP1306 SAMURAI14

Energy Technology Data Exchange (ETDEWEB)

Reichert, Sebastian [TU Munich (Germany); Collaboration: NP1306-SAMURAI14-Collaboration

2015-07-01

Violent stellar processes are currently assumed to be a major origin of the elements beyond iron and their abundances. The conditions during stellar explosions lead to the so called r-process in which the rapid capture of neutrons and subsequent β decays form heavier elements. This extension of the nuclei stops at the point when the repulsive Coulomb energy induces fission. Its recycling is one key aspect to describe the macroscopic structure of the r-process and the well known elemental abundance pattern. The RIBF at RIKEN is able to provide such neutron rich heavy element beams and a first test with the primary beam {sup 238}U was performed to understand the response of the SAMURAI spectrometer and detectors for heavy beams. The final goal is the definition of the fission barrier height with a resolution of 1 MeV (in σ) using the missing mass method using (p,2p) reactions in inverse kinematics.

Capture reactions of 40Ca and 48Ca with targets of 197Au and 208Pb

International Nuclear Information System (INIS)

Stokstad, R.; Chan, Y.; Chavez, E.

1988-03-01

The reactions of 40 Ca and 48 Ca with targets of 197 Au and 208 Pb have been measured in the region from below the interaction barrier to about twice the barrier energy. The fission-like fragments were detected in a pair of position-sensitive, multi-wire proportional counters and were identified from measurements of position and time using two-body kinematics. In the region above the barrier the cross sections for capture are less than those given by the touching condition, indicating that an /open quotes/extra push/close quotes/ is required to induce capture. The observations for 40 Ca and 48 Ca show different fissilities for the onset of the extra push and indicate that charge equilibration may be an important factor governing capture reactions. Below the barrier the cross sections show an enhancement relative to the prediction for a one dimensional barrier. The enhancements are larger for 40 Ca than for 48 Ca (for both targets) and this is in qualitative agreement with predictions based on the coupling of the relative motion to low-lying collective states. Both above and below the barrier, we find that the change in the light partner, from 48 Ca to 40 Ca, has a larger effect on the cross sections than the change from 208 Pb to 197 Au, after correction for the change in the Coulomb barrier. 16 refs., 7 figs

Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

Science.gov (United States)

Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

2012-01-01

Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

Directory of Open Access Journals (Sweden)

Ziya Kalay

Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

Science.gov (United States)

Asgharzadeh, Somaie; Vahedpour, Morteza

2018-06-01

Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

Patterns of reproductive isolation in a haplodiploid - strong post-mating, prezygotic barriers among three forms of a social spider mite.

Science.gov (United States)

Sato, Yukie; Sakamoto, Hironori; Gotoh, Tetsuo; Saito, Yutaka; Chao, Jung-Tai; Egas, Martijn; Mochizuki, Atsushi

2018-03-22

In speciation research, much attention is paid to the evolution of reproductive barriers, preventing diverging groups from hybridizing back into one gene pool. The prevalent view is that reproductive barriers evolve gradually as a by-product of genetic changes accumulated by natural selection and genetic drift in groups that are segregated spatially and/or temporally. Reproductive barriers, however, can also be reinforced by natural selection against maladaptive hybridization. These mutually compatible theories are both empirically supported by studies, analysing relationships between intensity of reproductive isolation and genetic distance in sympatric taxa and allopatric taxa. Here, we present the - to our knowledge - first comparative study in a haplodiploid organism, the social spider mite Stigmaeopsis miscanthi, by measuring premating and post-mating, pre- and post-zygotic components of reproductive isolation, using three recently diverged forms of the mite that partly overlap in home range. We carried out cross-experiments and measured genetic distances (mitochondrial DNA and nuclear DNA) among parapatric and allopatric populations of the three forms. Our results show that the three forms are reproductively isolated, despite the absence of premating barriers, and that the post-mating, prezygotic component contributes most to reproductive isolation. As expected, the strength of post-mating reproductive barriers positively correlated with genetic distance. We did not find a clear pattern of prezygotic barriers evolving faster in parapatry than in allopatry, although one form did show a trend in line with the ecological and behavioural relationships between the forms. Our study advocates the versatility of haplodiploid animals for investigating the evolution of reproductive barriers. © 2018 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2018 European Society For Evolutionary Biology.

Improved HEPA Filter Technology for Flexible and Rigid Containment Barriers

International Nuclear Information System (INIS)

Pinson, Paul Arthur

1998-01-01

Safety and reliability in glovebox operations can be significantly improved and waste packaging efficiencies can be increased by inserting flexible, lightweight, high capacity HEPA filters into the walls of plastic sheet barriers. This HEPA filter/barrier technology can be adapted to a wide variety of applications: disposable waste bags, protective environmental barriers for electronic equipment, single or multiple use glovebag assemblies, flexible glovebox wall elements, and room partitions. These reliable and inexpensive filtered barriers have many uses in fields such as radioactive waste processing, HVAC filter changeout, vapor or grit blasting, asbestos cleanup, pharmaceutical, medical, biological, and electronic equipment containment. The applications can result in significant cost savings, improved operational reliability and safety, and total waste volume reduction. This technology was developed at the Argonne National Laboratory-West (ANL-W) in 1993 and has been used at ANL-W since then at the TRU Waste Characterization Chamber Gloveboxes. Another 1998 AGS Conference paper titled ''TRU Waste Characterization Gloveboxes'', presented by Mr. David Duncan of ANL-W, describes these boxes

Understanding barriers to implementation of an adaptive land management program

Science.gov (United States)

Jacobson, S.K.; Morris, J.K.; Sanders, J.S.; Wiley, E.N.; Brooks, M.; Bennetts, R.E.; Percival, H.F.; Marynowski, S.

2006-01-01

communication barriers through interpersonal and electronic communication channels; (3) development of an OBVM external advisory committee; and (4) adoption of characteristics of an organizational culture that promotes flexibility and learning. ??2006 Society for Conservation Biology.

Recent developments in fusion and direct reactions with weakly bound nuclei

International Nuclear Information System (INIS)

Canto, L.F.; Gomes, P.R.S.; Donangelo, R.; Lubian, J.; Hussein, M.S.

2015-01-01

In this Report we give a balanced account of the experimental and theoretical advances acquired over the last decade in the field of near-barrier fusion reactions induced by weakly bound stable and unstable nuclei. The elastic scattering and breakup reactions of these systems are also extensively reviewed as they play an important role in the fusion process. We review several theoretical tools used in the description of the data. The concepts of Complete Fusion (CF), Incomplete Fusion (ICF) and Total Fusion (TF), which is the sum of CF and ICF, are discussed and recent work on the calculation of these quantities is reviewed. The Continuum Discretized Coupled Channels (CDCC) method and its semiclassical version are described in detail and their limitations are pointed out. More importantly, we describe the salient features of the conclusions reached from the more than 40 measurements made, over a decade, of near-barrier fusion, elastic scattering and breakup reactions, and confront these data with the CDCC or other methods appropriate for these processes at the energy regime in question.

Adaptive management in the context of barriers in European freshwater ecosystems

DEFF Research Database (Denmark)

Birnie-Gauvin, Kim; Tummers, Jeroen S.; Lucas, Martyn C.

2017-01-01

Many natural habitats have been modified to accommodate for the presence of humans and their needs. Infrastructures e such as hydroelectric dams, weirs, culverts and bridges e are now a common occurrence in streams and rivers across the world. As a result, freshwater ecosystems have been altered...... extensively, affecting both biological and geomorphological components of the habitats. Many fish species rely on these freshwater ecosystems to complete their lifecycles, and the presence of barriers has been shown to reduce their ability to migrate and sustain healthy populations. In the long run, barriers...... may have severe repercussions on population densities and dynamics of aquatic animal species. There is currently an urgent need to address these issues with adequate conservation approaches. Adaptive management provides a relevant approach to managing barriers in freshwater ecosystems as it addresses...

Classification of Recombinant Biologics in the EU

DEFF Research Database (Denmark)

Klein, Kevin; De Bruin, Marie L; Broekmans, Andre W

2015-01-01

BACKGROUND AND OBJECTIVE: Biological medicinal products (biologics) are subject to specific pharmacovigilance requirements to ensure that biologics are identifiable by brand name and batch number in adverse drug reaction (ADR) reports. Since Member States collect ADR data at the national level...... of biologics by national authorities responsible for ADR reporting. METHODS: A sample list of recombinant biologics from the European Medicines Agency database of European Public Assessment Reports was created to analyze five Member States (Belgium, the Netherlands, Spain, Sweden, and the UK) according...

Mechanism and kinetics of the electrocatalytic reaction responsible for the high cost of hydrogen fuel cells.

Science.gov (United States)

Cheng, Tao; Goddard, William A; An, Qi; Xiao, Hai; Merinov, Boris; Morozov, Sergey

2017-01-25

The sluggish oxygen reduction reaction (ORR) is a major impediment to the economic use of hydrogen fuel cells in transportation. In this work, we report the full ORR reaction mechanism for Pt(111) based on Quantum Mechanics (QM) based Reactive metadynamics (RμD) simulations including explicit water to obtain free energy reaction barriers at 298 K. The lowest energy pathway for 4 e - water formation is: first, *OOH formation; second, *OOH reduction to H 2 O and O*; third, O* hydrolysis using surface water to produce two *OH and finally *OH hydration to water. Water formation is the rate-determining step (RDS) for potentials above 0.87 Volt, the normal operating range. Considering the Eley-Rideal (ER) mechanism involving protons from the solvent, we predict the free energy reaction barrier at 298 K for water formation to be 0.25 eV for an external potential below U = 0.87 V and 0.41 eV at U = 1.23 V, in good agreement with experimental values of 0.22 eV and 0.44 eV, respectively. With the mechanism now fully understood, we can use this now validated methodology to examine the changes upon alloying and surface modifications to increase the rate by reducing the barrier for water formation.

Barrier mechanisms in the Drosophila blood-brain barrier

Directory of Open Access Journals (Sweden)

Samantha Jane Hindle

2014-12-01

Full Text Available The invertebrate blood-brain barrier field is growing at a rapid pace and, in recent years, studies have shown a physiologic and molecular complexity that has begun to rival its vertebrate counterpart. Novel mechanisms of paracellular barrier maintenance through GPCR signaling were the first demonstrations of the complex adaptive mechanisms of barrier physiology. Building upon this work, the integrity of the invertebrate blood-brain barrier has recently been shown to require coordinated function of all layers of the compound barrier structure, analogous to signaling between the layers of the vertebrate neurovascular unit. These findings strengthen the notion that many blood-brain barrier mechanisms are conserved between vertebrates and invertebrates, and suggest that novel findings in invertebrate model organisms will have a significant impact on the understanding of vertebrate BBB functions. In this vein, important roles in coordinating localized and systemic signaling to dictate organism development and growth are beginning to show how the blood-brain barrier can govern whole animal physiologies. This includes novel functions of blood-brain barrier gap junctions in orchestrating synchronized neuroblast proliferation, and of blood-brain barrier secreted antagonists of insulin receptor signaling. These advancements and others are pushing the field forward in exciting new directions. In this review, we provide a synopsis of invertebrate blood-brain barrier anatomy and physiology, with a focus on insights from the past 5 years, and highlight important areas for future study.

A scalable computational framework for establishing long-term behavior of stochastic reaction networks.

Directory of Open Access Journals (Sweden)

Ankit Gupta

2014-06-01

Full Text Available Reaction networks are systems in which the populations of a finite number of species evolve through predefined interactions. Such networks are found as modeling tools in many biological disciplines such as biochemistry, ecology, epidemiology, immunology, systems biology and synthetic biology. It is now well-established that, for small population sizes, stochastic models for biochemical reaction networks are necessary to capture randomness in the interactions. The tools for analyzing such models, however, still lag far behind their deterministic counterparts. In this paper, we bridge this gap by developing a constructive framework for examining the long-term behavior and stability properties of the reaction dynamics in a stochastic setting. In particular, we address the problems of determining ergodicity of the reaction dynamics, which is analogous to having a globally attracting fixed point for deterministic dynamics. We also examine when the statistical moments of the underlying process remain bounded with time and when they converge to their steady state values. The framework we develop relies on a blend of ideas from probability theory, linear algebra and optimization theory. We demonstrate that the stability properties of a wide class of biological networks can be assessed from our sufficient theoretical conditions that can be recast as efficient and scalable linear programs, well-known for their tractability. It is notably shown that the computational complexity is often linear in the number of species. We illustrate the validity, the efficiency and the wide applicability of our results on several reaction networks arising in biochemistry, systems biology, epidemiology and ecology. The biological implications of the results as well as an example of a non-ergodic biological network are also discussed.

Nitrogen inversion barriers affect the N-oxidation of tertiary alkylamines by cytochromes P450

DEFF Research Database (Denmark)

Rydberg, Patrik; Jørgensen, Martin S.; Jacobsen, T.A.

2013-01-01

Calculations: Cytochrome P450 enzymes facilitate a number of chemically different reactions. For example, amines can be either N-dealkylated or N-oxidized, but it is complex to rationalize which of these competing reactions occurs. It is shown that the barrier for inversion of the alkylamine...... nitrogen atom seems to be of vital importance for the amount of N-oxidized product formed relative to dealkylation and hydroxylation products....

Factors influencing the movement biology of migrant songbirds confronted with an ecological barrier

Science.gov (United States)

Smolinsky, J. A.; Diehl, Robert H.; Radzio, T. A.; Delaney, D. K.; Moore, F. R

2013-01-01

Whether or not a migratory songbird embarks on a long-distance flight across an ecological barrier is likely a response to a number of endogenous and exogenous factors. During autumn 2008 and 2009, we used automated radio tracking to investigate how energetic condition, age, and weather influenced the departure timing and direction of Swainson’s thrushes (Catharus ustulatus) during migratory stopover along the northern coast of the Gulf of Mexico. Most birds left within 1 h after sunset on the evening following capture. Those birds that departed later on the first night or remained longer than 1 day were lean. Birds that carried fat loads sufficient to cross the Gulf of Mexico generally departed in a seasonally appropriate southerly direction, whereas lean birds nearly always flew inland in a northerly direction. We did not detect an effect of age or weather on departures. The decision by lean birds to reorient movement inland may reflect the suitability of the coastal stopover site for deposition of fuel stores and the motivation to seek food among more extensive forested habitat away from the barrier.

Lagrangian descriptors of driven chemical reaction manifolds.

Science.gov (United States)

Craven, Galen T; Junginger, Andrej; Hernandez, Rigoberto

2017-08-01

The persistence of a transition state structure in systems driven by time-dependent environments allows the application of modern reaction rate theories to solution-phase and nonequilibrium chemical reactions. However, identifying this structure is problematic in driven systems and has been limited by theories built on series expansion about a saddle point. Recently, it has been shown that to obtain formally exact rates for reactions in thermal environments, a transition state trajectory must be constructed. Here, using optimized Lagrangian descriptors [G. T. Craven and R. Hernandez, Phys. Rev. Lett. 115, 148301 (2015)PRLTAO0031-900710.1103/PhysRevLett.115.148301], we obtain this so-called distinguished trajectory and the associated moving reaction manifolds on model energy surfaces subject to various driving and dissipative conditions. In particular, we demonstrate that this is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions. The development of these objects is paramount in the theory of reaction dynamics as the transition state structure and its underlying network of manifolds directly dictate reactivity and selectivity.

Electrode redox reactions with polarizable molecules

Science.gov (United States)

Matyushov, Dmitry V.

2018-04-01

A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

[On Atomic Nuclear Fusion Processes at Low-Temperatures. An Enhancement of the Probability of Transition through a Potential Barrier Due to the So-Called Barrier Anti-Zeno Effect].

Science.gov (United States)

Namiot, V A

2016-01-01

It is known that in quantum mechanics the act of observing the experiment can affect the experimental findings in some cases. In particular, it happens under the so-called Zeno effect. In this work it is shown that in contrast to the "standard" Zeno-effect where the act of observing a process reduces the probability of its reality, an inverse situation when a particle transmits through a potential barrier (a so-called barrier anti-Zeno effect) can be observed, the observation of the particle essentially increases the probability of its transmission through the barrier. The possibility of using the barrier anti-Zeno effect is discussed to explain paradoxical results of experiments on "cold nuclear fusion" observed in various systems including biological ones. (According to the observers who performed the observations, the energy generation, which could not be explained by any chemical processes, as well as the change in the isotope and even element composition of the studied object may occur in these systems.

Ion microbeam analysis. Application to the study of the skin barrier and its nano-toxicology

International Nuclear Information System (INIS)

Simon, M.

2009-12-01

This work is dedicated to the use of ion microbeam irradiation to the study of a complex biological tissue like skin. Up to now, it has been very difficult to detect and track metallic oxides and manufactured nano-particles in biological tissues, most particularly in skin. Thus, it is essential to precise the mechanisms involved in skin barrier function processes face to exogenous agents like nano-particles and to characterize them in biological models in vitro/in vivo. During my work, I have had the opportunity to combine quantitative methods of analysis with high resolution imagery techniques (confocal microscopy, transmission electron microscopy and ion beam analysis) in order to characterize: (i) the skin barrier function of an ex vivo pig ear skin model understanding the ion homeostasis behavior face to different chemical or physical stresses; (ii) the impact on viability, accumulation and intracellular distribution of nano-particles (Titanium Oxides) naked or functionalized with fluorescent dyes (FITC, Rhodamine)

Treatment of slaughter wastewater by coagulation sedimentation-anaerobic biological filter and biological contact oxidation process

Science.gov (United States)

Sun, M.; Yu, P. F.; Fu, J. X.; Ji, X. Q.; Jiang, T.

2017-08-01

The optimal process parameters and conditions for the treatment of slaughterhouse wastewater by coagulation sedimentation-AF - biological contact oxidation process were studied to solve the problem of high concentration organic wastewater treatment in the production of small and medium sized slaughter plants. The suitable water temperature and the optimum reaction time are determined by the experiment of precipitation to study the effect of filtration rate and reflux ratio on COD and SS in anaerobic biological filter and the effect of biofilm thickness and gas water ratio on NH3-N and COD in biological contact oxidation tank, and results show that the optimum temperature is 16-24°C, reaction time is 20 min in coagulating sedimentation, the optimum filtration rate is 0.6 m/h, and the optimum reflux ratio is 300% in anaerobic biological filter reactor. The most suitable biological film thickness range of 1.8-2.2 mm and the most suitable gas water ratio is 12:1-14:1 in biological contact oxidation pool. In the coupling process of continuous operation for 80 days, the average effluent’s mass concentrations of COD, TP and TN were 15.57 mg/L, 40 mg/L and 0.63 mg/L, the average removal rates were 98.93%, 86.10%, 88.95%, respectively. The coupling process has stable operation effect and good effluent quality, and is suitable for the industrial application.

Constructing New Bioorthogonal Reagents and Reactions.

Science.gov (United States)

Row, R David; Prescher, Jennifer A

2018-05-15

Chemical tools are transforming our understanding of biomolecules and living systems. Included in this group are bioorthogonal reagents-functional groups that are inert to most biological species, but can be selectively ligated with complementary probes, even in live cells and whole organisms. Applications of these tools have revealed fundamental new insights into biomolecule structure and function-information often beyond the reach of genetic approaches. In many cases, the knowledge gained from bioorthogonal probes has enabled new questions to be asked and innovative research to be pursued. Thus, the continued development and application of these tools promises to both refine our view of biological systems and facilitate new discoveries. Despite decades of achievements in bioorthogonal chemistry, limitations remain. Several reagents are too large or insufficiently stable for use in cellular environments. Many bioorthogonal groups also cross-react with one another, restricting them to singular tasks. In this Account, we describe our work to address some of the voids in the bioorthogonal toolbox. Our efforts to date have focused on small reagents with a high degree of tunability: cyclopropenes, triazines, and cyclopropenones. These motifs react selectively with complementary reagents, and their unique features are enabling new pursuits in biology. The Account is organized by common themes that emerged in our development of novel bioorthogonal reagents and reactions. First, natural product structures can serve as valuable starting points for probe design. Cyclopropene, triazine, and cyclopropenone motifs are all found in natural products, suggesting that they would be metabolically stable and compatible with a variety of living systems. Second, fine-tuning bioorthogonal reagents is essential for their successful translation to biological systems. Different applications demand different types of probes; thus, generating a collection of tools that span a continuum of

Extracting reaction networks from databases-opening Pandora's box.

Science.gov (United States)

Fearnley, Liam G; Davis, Melissa J; Ragan, Mark A; Nielsen, Lars K

2014-11-01

Large quantities of information describing the mechanisms of biological pathways continue to be collected in publicly available databases. At the same time, experiments have increased in scale, and biologists increasingly use pathways defined in online databases to interpret the results of experiments and generate hypotheses. Emerging computational techniques that exploit the rich biological information captured in reaction systems require formal standardized descriptions of pathways to extract these reaction networks and avoid the alternative: time-consuming and largely manual literature-based network reconstruction. Here, we systematically evaluate the effects of commonly used knowledge representations on the seemingly simple task of extracting a reaction network describing signal transduction from a pathway database. We show that this process is in fact surprisingly difficult, and the pathway representations adopted by various knowledge bases have dramatic consequences for reaction network extraction, connectivity, capture of pathway crosstalk and in the modelling of cell-cell interactions. Researchers constructing computational models built from automatically extracted reaction networks must therefore consider the issues we outline in this review to maximize the value of existing pathway knowledge. © The Author 2013. Published by Oxford University Press.

Barium diffusion in metallo-organic solution deposited barrier layers and Y1Ba2Cu3O7-x films

International Nuclear Information System (INIS)

Lipeles, R.A.; Leung, M.S.; Thiede, D.A.

1990-01-01

This paper reports on barium silicate and barium aluminate films that were studied for use as chemical reaction and diffusion barrier layers for Y 1 Ba 2 Cu 3 O 7-x (YBC) deposited on sapphire and fused silica substrates by the sol-gel technique. Depth profiling by secondary ion mass spectrometry (SIMS) was used to characterize the abruptness of the interfaces between the barrier layer and the YBC film as well as the barrier layer and the substrate. The authors found that barium aluminate films reacted with fused silica substrates forming a coarse-grained barium silicate phase. Barium silicate, BaSiO 3 , also reacted with silica substrates forming a broad, amorphous reaction zone containing some BaSi 2 O 5 . Although barium silicate and barium aluminate deposited on sapphire formed a BaAl 12 O 19 phase, they provided a barrier to barium diffusion from sol-gel deposited YBC. Crystalline barium aluminate grown on c-cut sapphire was the most effective barrier layer for the growth of YBC films; compositionally uniform YBC films were made similar to that grown on strontium titanate substrates. These data show that chemically stable, crystalline films are more effective barrier layers than amorphous films

Splendor and misery of the distorted wave method applied to heavy ions transfer reactions

International Nuclear Information System (INIS)

Mermaz, M.C.

1979-01-01

The success and failure of the Distorted Wave Method (DWM) applied to heavy ion transfer reactions are illustrated by few examples: one and multi-nucleon transfer reactions induced by 15 N and 18 O on 28 Si target nucleus performed on the vicinity of Coulomb barrier respectively at 44 and 56 MeV incident energy

Biologically mediated dissolution of volcanic glass in seawater

NARCIS (Netherlands)

Staudigel, H; Yayanos, A; Chastain, R; Davies, G.T.; Verdurmen, E.A Th; Schiffmann, P; Bourcier, R; de Baar, H.J.W.

1998-01-01

We studied the effects of biological mediation on the dissolution of basaltic glass in seawater. Experiments with typical seawater microbial populations were contrasted with a sterile control, and reactions were monitored chemically and isotopically. Biologically mediated experiments produce twice

Mechanism of C-C and C-H bond cleavage in ethanol oxidation reaction on Cu2O(111): a DFT-D and DFT+U study.

Science.gov (United States)

Xu, Han; Miao, Bei; Zhang, Minhua; Chen, Yifei; Wang, Lichang

2017-10-04

The performance of transition metal catalysts for ethanol oxidation reaction (EOR) in direct ethanol fuel cells (DEFCs) may be greatly affected by their oxidation. However, the specific effect and catalytic mechanism for EOR of transition metal oxides are still unclear and deserve in-depth exploitation. Copper as a potential anode catalyst can be easily oxidized in air. Thus, in this study, we investigated C-C and C-H bond cleavage reactions of CH x CO (x = 1, 2, 3) species in EOR on Cu 2 O(111) using PBE+U calculations, as well as the specific effect of +U correction on the process of adsorption and reaction on Cu 2 O(111). It was revealed that the catalytic performance of Cu 2 O(111) for EOR was restrained compared with that of Cu(100). Except for the C-H cleavage of CH 2 CO, all the reaction barriers for C-C and C-H cleavage were higher than those on Cu(100). The most probable pathway for CH 3 CO to CHCO on Cu 2 O(111) was the continuous dehydrogenation reaction. Besides, the barrier for C-C bond cleavage increased due to the loss of H atoms in the intermediate. Moreover, by the comparison of the traditional GGA/PBE method and the PBE+U method, it could be concluded that C-C cleavage barriers would be underestimated without +U correction, while C-H cleavage barriers would be overestimated. +U correction was proved to be necessary, and the reaction barriers and the values of the Hubbard U parameter had a proper linear relationship.

Applications of a post-column fluorigenic reaction in liquid chromatography for the determination of glucose and fructose in biological matrices

International Nuclear Information System (INIS)

Coquet, A.; Veuthey, J.-L.; Haerdi, W.; Degli Agosti, R.

1991-01-01

A post-column fluorigenic reaction with benzamidine coupled to liquid chromatographic separation was used for the determination of reducing carbohydrates in three complex biological samples. This method allows the simultaneous determination of the different reducing sugars, which represent an improvement over batch enzymatic tests where in most instances only single monosaccharides can be determined. This selective liquid chromatographic method has a broad linear range. The method was validated by simultaneous analyses with a specific enzymatic test for glucose. Results are presented for the determination of glucose in human serum and mustard plants and glucose and fructose in white wines. (author). 14 refs.; 3 figs.; 3 tabs

From microscopic to macroscopic dynamics in mean-field theory: effect of neutron skin on fusion barrier and dissipation

Energy Technology Data Exchange (ETDEWEB)

Lacroix, D

2001-07-01

In this work, we introduce a method to reduce the microscopic mean-field theory to a classical macroscopic dynamics at the initial stage of fusion reaction. We show that TDHF (Time-dependent Hartree-Fock) could be a useful tool to infer information on the fusion barrier as well as on one-body dissipation effect. We apply the reduction of information to the case of head-on reaction between a {sup 16}O and {sup 16,22,24,28}O in order to quantify the effect of neutron skin on fusion. We show that the precise determination of fusion barrier requires, in addition to the relative distance between center of mass, the introduction of an additional collective coordinate that explicitly breaks the neutron-proton symmetry. With this additional collective variable, we obtain a rather precise determination of the barrier position, height and diffuseness as well as one-body friction. (author)

Nuclear chain reaction: forty years later

International Nuclear Information System (INIS)

Sachs, R.G.

1984-01-01

The proceedings from a 1982 symposium 40 years after the first controlled nuclear chain reaction took place in Chicago covers four sessions and public discussion. The session covered the history of the chain reaction; peaceful uses in technology, medicine, and biological science; peaceful uses in power generation; and nuclear weapons control. Among the speakers were Eugene Wigner, Glenn Seaborg, Alvin Weinberg, and others who participated in the first chain reaction experiments. The proceedings reflect differences of opinion among the scientists as well as the general public. References, slides, and tables used to illustrate the individual talks are included with the papers

Nucleophilic ring opening reactions of aziridines.

Science.gov (United States)

Akhtar, Rabia; Naqvi, Syed Ali Raza; Zahoor, Ameer Fawad; Saleem, Sameera

2018-05-04

Aziridine ring opening reactions have gained tremendous importance in the synthesis of nitrogen containing biologically active molecules. During recent years, a great effort has been put forward by scientists toward unique bond construction methodologies via ring opening of aziridines. In this regard, a wide range of chiral metal- and organo-catalyzed desymmetrization reactions of aziridines have been reported with carbon, sulfur, oxygen, nitrogen, halogen, and other nucleophiles. In this review, an outline of methodologies adopted by a number of scientists during 2013-2017 for aziridine ring opening reactions as well as their synthetic applications is described.

Finite-time barriers to front propagation in two-dimensional fluid flows

Science.gov (United States)

Mahoney, John R.; Mitchell, Kevin A.

2015-08-01

Recent theoretical and experimental investigations have demonstrated the role of certain invariant manifolds, termed burning invariant manifolds (BIMs), as one-way dynamical barriers to reaction fronts propagating within a flowing fluid. These barriers form one-dimensional curves in a two-dimensional fluid flow. In prior studies, the fluid velocity field was required to be either time-independent or time-periodic. In the present study, we develop an approach to identify prominent one-way barriers based only on fluid velocity data over a finite time interval, which may have arbitrary time-dependence. We call such a barrier a burning Lagrangian coherent structure (bLCS) in analogy to Lagrangian coherent structures (LCSs) commonly used in passive advection. Our approach is based on the variational formulation of LCSs using curves of stationary "Lagrangian shear," introduced by Farazmand et al. [Physica D 278-279, 44 (2014)] in the context of passive advection. We numerically validate our technique by demonstrating that the bLCS closely tracks the BIM for a time-independent, double-vortex channel flow with an opposing "wind."

Quantifying atom addition reactions on amorphous solid water: a review of recent laboratory advances

Science.gov (United States)

He, Jiao; Vidali, Gianfranco

2018-06-01

Complex organic molecules found in space are mostly formed on and in the ice mantle covering interstellar dust grains. In clouds where ionizing irradiation is insignificant, chemical reactions on the ice mantle are dominated by thermal processes. Modeling of grain surface chemistry requires detailed information from the laboratory, including sticking coefficients, binding energies, diffusion energy barriers, mechanism of reaction, and chemical desorption rates. In this talk, recent laboratory advances in obtaining these information would be reviewed. Specifically, this talk will focus on the efforts in our group in: 1) Determining the mechanism of atomic hydrogen addition reactions on amorphous solid water (ASW); 2) Measuring the chemical desorption coefficient of H+O3-->O2+OH using the time-resolved scattering technique; and 3) Measuring the diffusion energy barrier of volatile molecules on ASW. Further laboratory studies will be suggested.This research was supported by NSF Astronomy & Astrophysics Research Grant #1615897.

First time evidence of pronounced plateaus right above the Coulomb barrier in 8Li + 4He fusion

Directory of Open Access Journals (Sweden)

A. Del Zoppo

2016-02-01

Full Text Available We investigate unprecedented experimental information on the fusion reaction induced by the radioactive projectile 8Li on a 4He gas target, at center-of-mass energies between 0.6 and 5 MeV. The main issue is the tendency of the dimensionless fusion cross section σfπƛ2 to form well visible plateaus alternated to steep rises. This finding is likely to be the most genuine consequence of the discrete nature of the intervening angular momenta observed so far in fusion reactions right above the Coulomb barrier. A partial-wave analysis, exclusively based on a pure quantal penetration fusion model and sensitive to the interaction potential, identifies a remarkably low-height barrier.

Physics and biology

International Nuclear Information System (INIS)

Frauenfelder, H.

1988-01-01

The author points out that the coupling between physics and biology is becoming closer as time goes on. He tries to show that physical studies on biological systems not only yield insight into biology but also provide results of interest to physics. Biological systems are extremly complex system. Ideally one would like to understand the behavior of such systems in terms of the behavior of its constituent atoms. Since in small organisms this may be 10 20 atoms, it is clear these are not simple many-body systems. He reviews the basic elements of cells and then considers the broader questions of structure, complexity, and function, which must be looked at on levels from the cell to the organism. Despite the vast amount of observational material already in existence, biophysics and biological physics are only at a beginning. We can expect that physics will continue to interact strongly with biology. Actually, the connection also includes chemistry and mathematics. New tools that become available in physics will continue to be applied to biological problems. We can expect that the flow of information will not be one way; biological systems will provide new information on many old and new parts of physics, from reaction theory and transport phenomena to complexity, cooperativity, and nonlinear processes

Comparison of one and two-neutron transfer near the Coulomb barrier for the 27Al(18O, 16O)29Al, 27Al(18O, 17O)28Al and 27Al(13C, 12C)28Al reactions

International Nuclear Information System (INIS)

Schiller, S.A.; Eck, J.S.

1975-01-01

Total reaction cross sections for the transfer reactions 27 Al( 18 O, 16 O) 29 Al, 27 Al( 18 O, 17 O) 28 Al and 27 Al( 13 C, 12 C) 28 Al are reported for center-of-mass energies between 13 and 20 MeV for 18 O projectiles and between 11 and 17.5 MeV for 13 C projectiles. The reaction products, 29 Al, and 28 Al, beta decay to 29 Si and 28 Si, respectively, and the subsequent γ decays of 29 Si and 28 Si were measured. Due to the relatively long beta decay half lives, data were taken in a beam-off mode, resulting in very clean spectra. Total cross sections were calculated and compared with a theoretical model for barrier penetration proposed by C.Y. Wong. Differences between 18 O induced one and two-neutron total transfer reaction cross sections are discussed. (orig.) [de

Investigation of barriers to clinical practice guideline-recommended pharmacotherapy in the treatment of COPD.

Directory of Open Access Journals (Sweden)

Price L

2007-06-01

Full Text Available Background: The adoption of clinical practice guideline recommendations for COPD is suboptimal. Determining the barriers to the implementation of these practice guidelines may help improve patient care.Objective: To determine whether barriers to the use of pharmacotherapy according to practice guidelines are related primarily to patient or prescriber factors.Methods: Retrospective cohort study. Members of a health maintenance organization identified as having spirometry-defined COPD ranging from stage II to IV. Electronic medical records were reviewed for documentation of the following: 1 patient affordability issues, 2 history of an adverse drug reaction, 3 history of inefficacy to therapy, and 4 prescription history.Results: A total of 111 medical records were reviewed. There were 51% of patients who had not filled medications that had been prescribed in accordance with guidelines and 43% did not have the guideline recommended medications prescribed in the previous year. Only 4% and 2% of patients had documented inefficacy and affordability issues, respectively. There were no reported cases of adverse drug reactions. Conclusions: This study provides insight to the acceptance of COPD treatment recommendations by patients and providers. Further research is needed to design interventions to reduce barriers and optimize COPD treatment.

APUAMA: a software tool for reaction rate calculations.

Science.gov (United States)

Euclides, Henrique O; P Barreto, Patricia R

2017-06-01

APUAMA is a free software designed to determine the reaction rate and thermodynamic properties of chemical species of a reagent system. With data from electronic structure calculations, the APUAMA determine the rate constant with tunneling correction, such as Wigner, Eckart and small curvature, and also, include the rovibrational level of diatomic molecules. The results are presented in the form of Arrhenius-Kooij form, for the reaction rate, and the thermodynamic properties are written down in the polynomial form. The word APUAMA means "fast" in Tupi-Guarani Brazilian language, then the code calculates the reaction rate on a simple and intuitive graphic interface, the form fast and practical. As program output, there are several ASCII files with tabulated information for rate constant, rovibrational levels, energy barriers and enthalpy of reaction, Arrhenius-Kooij coefficient, and also, the option to the User save all graphics in BMP format.

Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

OpenAIRE

Rizvi, Masood Ahmad; Teshima, Norio; Maqsood, Syed Raashid; Akhoon, Showket Ahmad; Peerzada, Ghulam Mustafa

2015-01-01

Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III) redox reaction using spectrophotometric and potentiometric methods. The results were corroborated...

Stochastic processes, multiscale modeling, and numerical methods for computational cellular biology

CERN Document Server

2017-01-01

This book focuses on the modeling and mathematical analysis of stochastic dynamical systems along with their simulations. The collected chapters will review fundamental and current topics and approaches to dynamical systems in cellular biology. This text aims to develop improved mathematical and computational methods with which to study biological processes. At the scale of a single cell, stochasticity becomes important due to low copy numbers of biological molecules, such as mRNA and proteins that take part in biochemical reactions driving cellular processes. When trying to describe such biological processes, the traditional deterministic models are often inadequate, precisely because of these low copy numbers. This book presents stochastic models, which are necessary to account for small particle numbers and extrinsic noise sources. The complexity of these models depend upon whether the biochemical reactions are diffusion-limited or reaction-limited. In the former case, one needs to adopt the framework of s...

A simple thermometric technique for reaction-rate determination of inorganic species, based on the iodide-catalysed cerium(IV)-arsenic(III) reaction.

Science.gov (United States)

Grases, F; Forteza, R; March, J G; Cerda, V

1985-02-01

A very simple reaction-rate thermometric technique is used for determination of iodide (5-20 ng ml ), based on its catalytic action on the cerium(IV)-arsenic(III) reaction, and for determination of mercury(II) (1.5-10 ng ml ) and silver(I) (2-10 ng ml ), based on their inhibitory effect on this reaction. The reaction is followed by measuring the rate of temperature increase. The method suffers from very few interferences and is applied to determination of iodide in biological and inorganic samples, and Hg(II) and Ag(I) in pharmaceutical products.

Influence of Nitrate on the Hanford 100D Area In Situ Redox Manipulation Barrier Longevity

International Nuclear Information System (INIS)

Szecsody, Jim E.; Phillips, Jerry L.; Vermeul, Vince R.; Fruchter, Jonathan S.; Williams, Mark D.

2005-01-01

The purpose of this laboratory study is to determine the influence of nitrate on the Hanford 100D Area in situ redox manipulation (ISRM) barrier longevity. There is a wide spread groundwater plume of 60 mg/L nitrate upgradient of the ISRM barrier with lower nitrate concentrations downgradient, suggestive of nitrate reduction occurring. Batch and 1-D column experiments showed that nitrate is being slowly reduced to nitrite and ammonia. These nitrate reduction reactions are predominantly abiotic, as experiments with and without bactericides present showed no difference in nitrate degradation rates. Nitrogen species transformation rates determined in experiments covered a range of ferrous iron/nitrate ratios such that the data can be used to predict rates in field scale conditions. Field scale reaction rate estimates for 100% reduced sediment (16 C) are: (a) nitrate degradation = 202 ± 50 h (half-life), (b) nitrite production = 850 ± 300 h, and (c) ammonia production = 650 ± 300 h. Calculation of the influence of nitrate reduction on the 100D Area reductive capacity requires consideration of mass balance and reaction rate effects. While dissolved oxygen and chromate reduction rates are rapid and essentially at equilibrium in the aquifer, nitrate transformation reactions are slow (100s of hours). In the limited (20-40 day) residence time in the ISRM barrier, only a portion of the nitrate will be reduced, whereas dissolved oxygen and chromate are reduced to completion. Assuming a groundwater flow rate of 1 ft/day, it is estimated that the ISRM barrier reductive capacity is 160 pore volumes (with no nitrate), and 85 pore volumes if 60 mg/L nitrate is present (i.e., a 47% decrease in the ISRM barrier longevity). Zones with more rapid groundwater flow will be less influenced by nitrate reduction. For example, a zone with a groundwater flow rate of 3 ft/day and 60 mg/L nitrate will have a reductive capacity of 130 pore volumes. Finally, long-term column experiments

Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

DEFF Research Database (Denmark)

Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten

2010-01-01

charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting...... reaction on Pt(111) to be Tafel−Volmer for HOR and Volmer−Tafel for HER. Calculated rates agree well with experimental data. Both the H adsorption energy and the energy barrier for the Tafel reaction are then calculated for a range of metal electrodes, including Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Ru, Re......, W, Mo, and Nb, different facets, and step of surfaces. We compare the results for different facets of the Pt electrode to experimental data. Our results suggest that the most important parameter for describing the HOR or the HER activity of an electrode is its binding free energy of H. We present...

Mass transfer with chemical reaction in multiphase systems

International Nuclear Information System (INIS)

Alper, E.

1983-01-01

These volumes deal with the phenomenon of 'mass transfer with chemical reaction' which is of industrial, biological and physiological importance. In process engineering, it is encountered both in separation processes and in reaction engineering and both aspects are covered here in four sections: introduction; gas-liquid system; liquid-liquid system; and gas-liquid-solid system

The formation of urea in space. I. Ion-molecule, neutral-neutral, and radical gas-phase reactions

Science.gov (United States)

Brigiano, Flavio Siro; Jeanvoine, Yannick; Largo, Antonio; Spezia, Riccardo

2018-02-01

Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N-C-O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C-O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims: We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods: We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results: Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.

Reaction mechanisms in 24.3 MeV/nucleon 238U induced reactions through a comprehensive study of fission

International Nuclear Information System (INIS)

Chbihi, A.; Galin; Guerreau, D.; Lewitowicz, M.; Morjean, M.; Pouthas, J.; Piasecki, E.; Kordyasz, A.; Iwanicki, J.; Jastrzebski, J.; Pienkowski, L.; Crema, E.; Gatty, B.; Jacquet, D.; Muchorowska, M.

1994-01-01

Nuclear reaction mechanisms for system characterized by very different asymmetries (U+C, Si, Ni, Au) have been investigated at 24.3 MeV/nucleon, using as observables both the fission products and the neutron multiplicity. It is clearly observed that the fusion process-whatever its completeness- can only occur with rather light target nuclei, indicating the persistence of potential energy effects much above the interaction barrier. (authors). 22 refs., 1 fig

Engineered barrier development for a nuclear waste repository in basalt: an integration of current knowledge

Energy Technology Data Exchange (ETDEWEB)

Smith, M.J.

1980-05-01

This document represents a compilation of data and interpretive studies conducted as part of the engineered barriers program of the Basalt Waste Isolation Project. The overall objective of these studies is to provide information on barrier system designs, emplacement and isolation techniques, and chemical reactions expected in a nuclear waste repository located in the basalts underlying the Hanford Site within the state of Washington. Backfills, waste-basalt interactions, sorption, borehole plugging, etc., are among the topics discussed.

Engineered barrier development for a nuclear waste repository in basalt: an integration of current knowledge

International Nuclear Information System (INIS)

Smith, M.J.

1980-05-01

This document represents a compilation of data and interpretive studies conducted as part of the engineered barriers program of the Basalt Waste Isolation Project. The overall objective of these studies is to provide information on barrier system designs, emplacement and isolation techniques, and chemical reactions expected in a nuclear waste repository located in the basalts underlying the Hanford Site within the state of Washington. Backfills, waste-basalt interactions, sorption, borehole plugging, etc., are among the topics discussed

Nucleon transfer reactions to rotational states induced by 206,208PB projectiles

International Nuclear Information System (INIS)

Wollersheim, H.J.; DeBoer, F.W.N.; Emling, H.; Grein, H.; Grosse, E.; Spreng, W.; Eckert, G.; Elze, Th.W.; Stelzer, K.; Lauterbach, Ch.

1986-01-01

In a systematic study of nucleon transfer reactions accompanied by Coulomb excitation the authors bombarded 152 Sm, 160 Gd and 232 Th with 206, 208 Pb beams at incident energies close to the Coulomb barrier. Particle-gamma coincidence techniques were used to identify excited states of reaction products populated through inelastic scattering and in nucleon transfer reactions. Large cross sections were observed for one- and two-neutron pick-up from 232 Th at an incident energy of 6.4 MeV/μ. The results are analyzed in the framework of semiclassical models

Solvent effect on the degree of (a)synchronicity in polar Diels-Alder reactions from the perspective of the reaction force constant analysis.

Science.gov (United States)

Yepes, Diana; Martínez-Araya, Jorge I; Jaque, Pablo

2017-12-29

In this work, we computationally evaluated the influence of six different molecular solvents, described as a polarizable continuum model at the M06-2X/6-31+G(d,p) level, on the activation barrier/reaction rate, overall energy change, TS geometry, and degree of (a)synchronicity of two concerted Diels-Alder cycloadditions of acrolein (R1) and its complex with Lewis acid acrolein···BH 3 (R2) to cyclopentadiene. In gas-phase, we found that both exothermicity and activation barrier are only reduced by about 2.0 kcal mol -1 , and the asynchronicity character of the mechanism is accentuated when BH 3 is included. An increment in the solvent's polarity lowers the activation energy of R1 by 1.3 kcal mol -1 , while for R2 the reaction rate is enhanced by more than 2000 times at room temperature (i.e., the activation energy decreases by 4.5 kcal mol -1 ) if the highest polar media is employed. Therefore, a synergistic effect is achieved when both external agents, i.e., Lewis acid catalyst and polar solvent, are included together. This effect was ascribed to the ability of the solvent to favor the encounter between cyclopentadiene and acrolein···BH 3 . This was validated by the asymmetry of the TS which becomes highly pronounced when either both or just BH 3 is considered or the solvent's polarity is increased. Finally, the reaction force constant κ(ξ) reveals that an increment in the solvent's polarity is able to turn a moderate asynchronous mechanism of the formation of the new C-C σ-bonds into a highly asynchronous one. Graphical abstract A synergistic effect is achieved when both external agents, i.e., Lewis acid catalyst and polar solvent, are included together: lowered energy barriers and increased asynchronicities.

Estimation of parameter sensitivities for stochastic reaction networks

KAUST Repository

Gupta, Ankit

2016-01-07

Quantification of the effects of parameter uncertainty is an important and challenging problem in Systems Biology. We consider this problem in the context of stochastic models of biochemical reaction networks where the dynamics is described as a continuous-time Markov chain whose states represent the molecular counts of various species. For such models, effects of parameter uncertainty are often quantified by estimating the infinitesimal sensitivities of some observables with respect to model parameters. The aim of this talk is to present a holistic approach towards this problem of estimating parameter sensitivities for stochastic reaction networks. Our approach is based on a generic formula which allows us to construct efficient estimators for parameter sensitivity using simulations of the underlying model. We will discuss how novel simulation techniques, such as tau-leaping approximations, multi-level methods etc. can be easily integrated with our approach and how one can deal with stiff reaction networks where reactions span multiple time-scales. We will demonstrate the efficiency and applicability of our approach using many examples from the biological literature.

Widespread horizontal genomic exchange does not erode species barriers among sympatric ducks

NARCIS (Netherlands)

Kraus, R.H.S.; Kerstens, H.H.D.; Hooft, van W.F.; Megens, H.J.W.C.; Elmberg, J.; Tsvey, A.; Sartakov, D.; Soloviev, S.A.; Crooijmans, R.P.M.A.; Groenen, M.A.M.; Ydenberg, R.C.; Prins, H.H.T.

2012-01-01

The study of speciation and maintenance of species barriers is at the core of evolutionary biology. During speciation the genome of one population becomes separated from other populations of the same species, which may lead to genomic incompatibility with time. This separation is complete when no

Properties of PTFE tape as a semipermeable membrane in fluorous reactions

Directory of Open Access Journals (Sweden)

Brendon A. Parsons

2015-06-01

Full Text Available In a PTFE tape phase-vanishing reaction (PV-PTFE, a delivery tube sealed with PTFE tape is inserted into a vessel which contains the substrate. The reagent diffuses across the PTFE tape barrier into the reaction vessel. PTFE co-polymer films have been found to exhibit selective permeability towards organic compounds, which was affected by the presence of solvents. In this study, we attempted to establish general trends of permeability of PTFE tape to different compounds and to better describe the process of solvent transport in PV-PTFE bromination reactions. Though PTFE tape has been reported as impermeable to some compounds, such as dimethyl phthalate, solvent adsorption to the tape altered its permeability and allowed diffusion through channels of solvent within the PTFE tape. In this case, the solvent-filled pores of the PTFE tape are chemically more akin to the adsorbed solvent rather than to the PTFE fluorous structure. The solvent uptake effect, which was frequently observed in the course of PV-PTFE reactions, can be related to the surface tension of the solvent and the polarity of the solvent relative to the reagent. The lack of pores in bulk PTFE prevents solvents from altering its permeability and, therefore, bulk PTFE is impermeable to most solvents and reagents. However, bromine, which is soluble in liquid fluorous media, diffused through the bulk PTFE. A better understanding of the PTFE phase barrier will make it possible to further optimize the PV-PTFE reaction design.

Toward High School Biology: Helping Middle School Students Understand Chemical Reactions and Conservation of Mass in Nonliving and Living Systems.

Science.gov (United States)

Herrmann-Abell, Cari F; Koppal, Mary; Roseman, Jo Ellen

2016-01-01

Modern biology has become increasingly molecular in nature, requiring students to understand basic chemical concepts. Studies show, however, that many students fail to grasp ideas about atom rearrangement and conservation during chemical reactions or the application of these ideas to biological systems. To help provide students with a better foundation, we used research-based design principles and collaborated in the development of a curricular intervention that applies chemistry ideas to living and nonliving contexts. Six eighth grade teachers and their students participated in a test of the unit during the Spring of 2013. Two of the teachers had used an earlier version of the unit the previous spring. The other four teachers were randomly assigned either to implement the unit or to continue teaching the same content using existing materials. Pre- and posttests were administered, and the data were analyzed using Rasch modeling and hierarchical linear modeling. The results showed that, when controlling for pretest score, gender, language, and ethnicity, students who used the curricular intervention performed better on the posttest than the students using existing materials. Additionally, students who participated in the intervention held fewer misconceptions. These results demonstrate the unit's promise in improving students' understanding of the targeted ideas. © 2016 C. F. Herrmann-Abell et al. CBE—Life Sciences Education © 2016 The American Society for Cell Biology. This article is distributed by The American Society for Cell Biology under license from the author(s). It is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

Fusion and quasifission studies for the 40Ca+186W,192Os reactions

Science.gov (United States)

Prasad, E.; Hinde, D. J.; Williams, E.; Dasgupta, M.; Carter, I. P.; Cook, K. J.; Jeung, D. Y.; Luong, D. H.; Palshetkar, C. S.; Rafferty, D. C.; Ramachandran, K.; Simenel, C.; Wakhle, A.

2017-09-01

Background: All elements above atomic number 113 have been synthesized using hot fusion reactions with calcium beams on statically deformed actinide target nuclei. Quasifission and fusion-fission are the two major mechanisms responsible for the very low production cross sections of superheavy elements. Purpose: To achieve a quantitative measurement of capture and quasifission characteristics as a function of beam energy in reactions forming heavy compound systems using calcium beams as projectiles. Methods: Fission fragment mass-angle distributions were measured for the two reactions 40Ca+186W and 40C+192Os, populating 226Pu and 232Cm compound nuclei, respectively, using the Heavy Ion Accelerator Facility and CUBE spectrometer at the Australian National University. Mass ratio distributions, angular distributions, and total fission cross sections were obtained from the experimental data. Simulations to match the features of the experimental mass-angle distributions were performed using a classical phenomenological approach. Results: Both 40Ca+186W and 40C+192Os reactions show strong mass-angle correlations at all energies measured. A maximum fusion probability of 60 -70 % is estimated for the two reactions in the energy range of the present study. Coupled-channels calculations assuming standard Woods-Saxon potential parameters overpredict the capture cross sections. Large nuclear potential diffuseness parameters ˜1.5 fm are required to fit the total capture cross sections. The presence of a weak mass-asymmetric quasifission component attributed to the higher angular momentum events can be reproduced with a shorter average sticking time but longer mass-equilibration time constant. Conclusions: The deduced above-barrier capture cross sections suggest that the dissipative processes are already occurring outside the capture barrier. The mass-angle correlations indicate that a compact shape is not achieved for deformation aligned collisions with lower capture barriers

Pycellerator: an arrow-based reaction-like modelling language for biological simulations.

Science.gov (United States)

Shapiro, Bruce E; Mjolsness, Eric

2016-02-15

We introduce Pycellerator, a Python library for reading Cellerator arrow notation from standard text files, conversion to differential equations, generating stand-alone Python solvers, and optionally running and plotting the solutions. All of the original Cellerator arrows, which represent reactions ranging from mass action, Michales-Menten-Henri (MMH) and Gene-Regulation (GRN) to Monod-Wyman-Changeaux (MWC), user defined reactions and enzymatic expansions (KMech), were previously represented with the Mathematica extended character set. These are now typed as reaction-like commands in ASCII text files that are read by Pycellerator, which includes a Python command line interface (CLI), a Python application programming interface (API) and an iPython notebook interface. Cellerator reaction arrows are now input in text files. The arrows are parsed by Pycellerator and translated into differential equations in Python, and Python code is automatically generated to solve the system. Time courses are produced by executing the auto-generated Python code. Users have full freedom to modify the solver and utilize the complete set of standard Python tools. The new libraries are completely independent of the old Cellerator software and do not require Mathematica. All software is available (GPL) from the github repository at https://github.com/biomathman/pycellerator/releases. Details, including installation instructions and a glossary of acronyms and terms, are given in the Supplementary information. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Reactive Transport and Coupled THM Processes in Engineering Barrier Systems (EBS)

International Nuclear Information System (INIS)

Steefel, Carl; Rutqvist, Jonny; Tsang, Chin-Fu; Liu, Hui-Hai; Sonnenthal, Eric; Houseworth, Jim; Birkholzer, Jens

2010-01-01

Geological repositories for disposal of high-level nuclear wastes generally rely on a multi-barrier system to isolate radioactive wastes from the biosphere. The multi-barrier system typically consists of a natural barrier system, including repository host rock and its surrounding subsurface environment, and an engineering barrier system (EBS). EBS represents the man-made, engineered materials placed within a repository, including the waste form, waste canisters, buffer materials, backfill and seals (OECD, 2003). EBS plays a significant role in the containment and long-term retardation of radionuclide release. EBS is involved in complex thermal, hydrogeological, mechanical, chemical and biological processes, such as heat release due to radionuclide decay, multiphase flow (including gas release due to canister corrosion), swelling of buffer materials, radionuclide diffusive transport, waste dissolution and chemical reactions. All these processes are related to each other. An in-depth understanding of these coupled processes is critical for the performance assessment (PA) for EBS and the entire repository. Within the EBS group of Used Fuel Disposition (UFD) Campaign, LBNL is currently focused on (1) thermal-hydraulic-mechanical-chemical (THMC) processes in buffer materials (bentonite) and (2) diffusive transport in EBS associated with clay host rock, with a long-term goal to develop a full understanding of (and needed modeling capabilities to simulate) impacts of coupled processes on radionuclide transport in different components of EBS, as well as the interaction between near-field host rock (e.g., clay) and EBS and how they effect radionuclide release. This final report documents the progress that LBNL has made in its focus areas. Specifically, Section 2 summarizes progress on literature review for THMC processes and reactive-diffusive radionuclide transport in bentonite. The literature review provides a picture of the state-of-the-art of the relevant research areas

Reactive Transport and Coupled THM Processes in Engineering Barrier Systems (EBS)

Energy Technology Data Exchange (ETDEWEB)

Steefel, Carl; Rutqvist, Jonny; Tsang, Chin-Fu; Liu, Hui-Hai; Sonnenthal, Eric; Houseworth, Jim; Birkholzer, Jens

2010-08-31

Geological repositories for disposal of high-level nuclear wastes generally rely on a multi-barrier system to isolate radioactive wastes from the biosphere. The multi-barrier system typically consists of a natural barrier system, including repository host rock and its surrounding subsurface environment, and an engineering barrier system (EBS). EBS represents the man-made, engineered materials placed within a repository, including the waste form, waste canisters, buffer materials, backfill and seals (OECD, 2003). EBS plays a significant role in the containment and long-term retardation of radionuclide release. EBS is involved in complex thermal, hydrogeological, mechanical, chemical and biological processes, such as heat release due to radionuclide decay, multiphase flow (including gas release due to canister corrosion), swelling of buffer materials, radionuclide diffusive transport, waste dissolution and chemical reactions. All these processes are related to each other. An in-depth understanding of these coupled processes is critical for the performance assessment (PA) for EBS and the entire repository. Within the EBS group of Used Fuel Disposition (UFD) Campaign, LBNL is currently focused on (1) thermal-hydraulic-mechanical-chemical (THMC) processes in buffer materials (bentonite) and (2) diffusive transport in EBS associated with clay host rock, with a long-term goal to develop a full understanding of (and needed modeling capabilities to simulate) impacts of coupled processes on radionuclide transport in different components of EBS, as well as the interaction between near-field host rock (e.g., clay) and EBS and how they effect radionuclide release. This final report documents the progress that LBNL has made in its focus areas. Specifically, Section 2 summarizes progress on literature review for THMC processes and reactive-diffusive radionuclide transport in bentonite. The literature review provides a picture of the state-of-the-art of the relevant research areas

Investigation of aluminised steel as a barrier to tritium using accelerator-based and hydrogen permeation techniques

Energy Technology Data Exchange (ETDEWEB)

Sokhi, R S; Forcey, K S; Ross, D K; Earwaker, L G [Birmingham Univ. (UK). School of Physics and Space Research

1989-04-01

Aluminised steel has been proposed as a barrier to tritium permeation in fusion reactors. The properties of these materials as tritium barriers have been studied using accelerator-based techniques and hydrogen permeation methods. The aluminide layers has been characterised by Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA) techniques using the 3 MV Dynamitron accelerator based at the School of Physics and Space Research Radiation Centre. The effectiveness of the aluminide layer as a tritium barrier has been measured directly by a conventional permeation apparatus over a range of temperatures. The effect of high temperatures on the structure of the aluminide layer has been examined. Any correlation between the composition of the layer and its effectiveness as a tritium barrier is also discussed. (orig.).

Behavioral Economics and the Public Acceptance of Synthetic Biology.

Science.gov (United States)

Oliver, Adam

2018-01-01

Different applications of synthetic biology are alike in that their possible negative consequences are highly uncertain, potentially catastrophic, and perhaps irreversible; therefore, they are also alike in that public attitudes about them are fertile ground for behavioral economic phenomena. Findings from behavioral economics suggest that people may not respond to such applications according to the normal rules of economic evaluation, by which the value of an outcome is multiplied by the mathematical probability that the outcome will occur. Possibly, then, synthetic biology applications challenge the normative postulates of the standard approach, too. I want to first consider how some of the phenomena described by behavioral economists-and behavioral scientists more broadly-might affect people's perceptions of the uncertainties associated with synthetic biology. My analysis will be far from complete, however, because behavioral economics is essentially the study of human behavior, and thus its reach is potentially vast and its development longstanding and ongoing. Nonetheless, I hope to give an indicative perspective on how some aspects of behavioral economics might affect the assessment and perceived acceptability of synthetic biology. I will then consider the issue of agency. Should policy-makers respect people's reactions to synthetic biology when those reactions are known to be driven by behavioral economic phenomena rather than following the normative postulates of rational choice theory? Or should policy-makers dismiss these reactions as inherently biased? I will argue that the normative force of these human reactions (probably) depends on phenomenon and context. © 2018 The Hastings Center.

Chemical Ligation Reactions of Oligonucleotides for Biological and Medicinal Applications.

Science.gov (United States)

Abe, Hiroshi; Kimura, Yasuaki

2018-01-01

Chemical ligation of oligonucleotides (ONs) is the key reaction for various ON-based technologies. We have tried to solve the problems of RNA interference (RNAi) technology by applying ON chemical ligation to RNAi. We designed a new RNAi system, called intracellular buildup RNAi (IBR-RNAi), where the RNA fragments are built up into active small-interference RNA (siRNA) in cells through a chemical ligation reaction. Using the phosphorothioate and iodoacetyl groups as reactive functional groups for the ligation, we achieved RNAi effects without inducing immune responses. Additionally, we developed a new chemical ligation for IBR-RNAi, which affords a more native-like structure in the ligated product. The new ligation method should be useful not only for IBR-RNAi but also for the chemical synthesis of biofunctional ONs.

Ruthenium nanocatalysis on redox reactions.

Science.gov (United States)

Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

2013-07-01

Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

Flow-through biological conversion of lignocellulosic biomass

Science.gov (United States)

Herring, Christopher D.; Liu, Chaogang; Bardsley, John

2014-07-01

The present invention is directed to a process for biologically converting carbohydrates from lignocellulosic biomass comprising the steps of: suspending lignocellulosic biomass in a flow-through reactor, passing a reaction solution into the reactor, wherein the solution is absorbed into the biomass substrate and at least a portion of the solution migrates through said biomass substrate to a liquid reservoir, recirculating the reaction solution in the liquid reservoir at least once to be absorbed into and migrate through the biomass substrate again. The biological converting of the may involve hydrolyzing cellulose, hemicellulose, or a combination thereof to form oligosaccharides, monomelic sugars, or a combination thereof; fermenting oligosaccharides, monomelic sugars, or a combination thereof to produce ethanol, or a combination thereof. The process can further comprise removing the reaction solution and processing the solution to separate the ethanol produced from non-fermented solids.

Adsorption and surface reaction of bis-diethylaminosilane as a Si precursor on an OH-terminated Si (0 0 1) surface

International Nuclear Information System (INIS)

Baek, Seung-Bin; Kim, Dae-Hee; Kim, Yeong-Cheol

2012-01-01

The adsorption and the surface reaction of bis-diethylaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 , BDEAS) as a Si precursor on an OH-terminated Si (0 0 1) surface were investigated to understand the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory. The bond dissociation energies between two atoms in BDEAS increased in the order of Si-H, Si-N, and the rest of the bonds. Therefore, the relatively weak Si-H and Si-N bonds were considered for bond breaking during the surface reaction. Optimum locations of BDEAS for the Si-H and Si-N bond breaking were determined on the surface, and adsorption energies of 0.43 and 0.60 eV, respectively, were obtained. The Si-H bond dissociation energy of the adsorbed BDEAS on the surface did not decrease, so that a high reaction energy barrier of 1.60 eV was required. On the other hand, the Si-N bond dissociation energy did decrease, so that a relatively low reaction energy barrier of 0.52 eV was required. When the surface reaction energy barrier was higher than the adsorption energy, BDEAS would be desorbed from the surface instead of being reacted. Therefore, the Si-N bond breaking would be dominantly involved during the surface reaction, and the result is in good agreement with the experimental data in the literature.

Biological mechanisms, one molecule at a time

Science.gov (United States)

Tinoco, Ignacio; Gonzalez, Ruben L.

2011-01-01

The last 15 years have witnessed the development of tools that allow the observation and manipulation of single molecules. The rapidly expanding application of these technologies for investigating biological systems of ever-increasing complexity is revolutionizing our ability to probe the mechanisms of biological reactions. Here, we compare the mechanistic information available from single-molecule experiments with the information typically obtained from ensemble studies and show how these two experimental approaches interface with each other. We next present a basic overview of the toolkit for observing and manipulating biology one molecule at a time. We close by presenting a case study demonstrating the impact that single-molecule approaches have had on our understanding of one of life's most fundamental biochemical reactions: the translation of a messenger RNA into its encoded protein by the ribosome. PMID:21685361

Evaluation of the AGCU Expressmarker 16 and 22 PCR Amplification Kits Using Biological Samples Applied to FTA Micro Cards in Reduced Volume Direct PCR Amplification Reactions

Directory of Open Access Journals (Sweden)

Samantha J Ogden

2015-01-01

Full Text Available This study evaluated the performance of the  Wuxi AGCU ScienTech Incorporation (HuiShan, Wuxi, China AGCU Expressmarker 16 (EX 16 and 22 (EX22 short tandem repeat (STR amplification kits in reduced reaction volumes using direct polymerase chain reaction (PCR amplification workflows. The commercially available PowerPlex® 21 (PP21 System (Promega, Wisconsin, USA, which follows similar direct workflows, was used as a reference. Anticoagulate blood applied to chemically impregnated  FTA TM Micro Cards (GE Healthcare UK Limited, Amersham Place, Little Chalfont, Buckinghamshire, HP7 9NA, UK was used to represent a complex biological sample. Allelic concordance, first-pass success rate, average peak heights, heterozygous peak height ratios (HPHRs, and intracolor and intercolor peak height balance were determined. In reduced volume PCR reactions, the performances of both the EX16 and EX22 STR amplification kits were comparable to that of the PP21 System. The level of performance was maintained at PCR reaction volumes, which are 40% of that recommended. The EX22 and PP21 System kits possess comparable overlapping genome coverage. This study evaluated the performance of the AGCU EX16 and EX22 STR amplification kits in reduced PCR reaction volumes using direct workflows in combination with whole blood applied to FTA TM Micro Cards. Allelic concordance, first-pass success rate, average peak heights, HPHRs, and intracolor and intercolor peak height balance were determined. A concordance analysis was completed that compared the performance of the EX16 and EX22 kits using human blood applied to FTA Micro Cards in combination with full, half, and reduced PCR reaction volumes. The PP21 System (Promega was used as a reference kit. Where appropriate, the distributions of data were assessed using the Shapiro-Wilk test. For normally-distributed data, statistics were calculated using analysis of variance (ANOVA and for nonparametric data the Wilcoxon

Aluminum oxide barrier coating on polyethersulfone substrate by atomic layer deposition for barrier property enhancement

International Nuclear Information System (INIS)

Kim, Hyun Gi; Kim, Sung Soo

2011-01-01

Aluminum oxide layers were deposited on flexible polyethersulfone (PES) substrates via plasma enhanced atomic layer deposition (PEALD) process using trimethylaluminum (TMA) and oxygen as precursor and reactant materials. Several process parameters in PEALD process were investigated in terms of refractive index and layer thickness. Number of process cycle increased the thickness and refractive index of the layer to enhance the barrier properties. Non-physisorbed TMA and unreacted oxygen were purged before and after the plasma reaction, respectively. Identical purge time was applied to TMA and oxygen and it was optimized for 10 s. Thinner and denser layer was formed as substrate temperature increased. However, the PES substrate could be deformed above 120 o C. Aluminum oxide layer formed on PES at optimized conditions have 11.8 nm of thickness and reduced water vapor transmission rate and oxygen transmission rate to below 4 x 10 -3 g/m 2 day and 4 x 10 -3 cm 3 /m 2 day, respectively. Polycarbonate and polyethylene naphthalate films were also tested at optimized conditions, and they also showed quite appreciable barrier properties to be used as plastic substrates.

Systematic study of sub-barrier fusion enhancement in heavy-ion reactions

Energy Technology Data Exchange (ETDEWEB)

Aguiar, C E; Aleixo, A N; Barbosa, V C; Canto, L F; Donangelo, R [Universidade Federal Rural do Rio de Janeiro (Brazil). Dept. de Fisica

1989-08-14

A systematic study of the heavy-ion fusion-cross-section enhancement at sub-barrier energies is carried out. The asymptotic energy shift introduced in a previous paper as a measure of this enhancement is considered from a theoretical point of view. It is claimed that this energy shift is composed of two terms: One of them is related to the bulk properties of nuclear matter, and the other corresponds to deviations depending on the specific nuclear structure of the collision partners. We show that the former can be approximately described by the neck-formation model for fusion and the latter is frequently a consequence of static deformation or vibrational excitation of the projectile and/or the target. A comparison of the neck-formation effects with those arising from neutron flow suggests that there is a connection between these two mechanisms. (orig.).

Barriers to involvement of men in ANC and VCT in Khayelitsha, South Africa.

Science.gov (United States)

Mohlala, Boshishi K F; Gregson, Simon; Boily, Marie-Claude

2012-01-01

We used qualitative methods to assess pregnant women and men's attitudes, feelings, beliefs, experiences and reactions to male partners' involvement in antenatal clinic (ANC) in Khayelitsha, Cape Town, South Africa. The aims of these studies were to determine barriers to male partners' attendance of ANC with their pregnant female partners and to identify possible strategies to overcome these barriers. Findings from the qualitative studies demonstrated that pregnant women were keen to invite their male sexual partners and that men would attend if invited. The main barrier to male participation was lack of awareness and the healthcare facility environment. The findings of these studies emphasized the need to increase awareness among men in Khayelitsha of the need for male attendance of ANC and the need to address the barriers to male attendance of ANC. It was clear that community sensitization programmes coupled with improvement of the health facility environment to be receptive to men are essential for increasing male attendance of ANC.

Redox-capacitor to connect electrochemistry to redox-biology.

Science.gov (United States)

Kim, Eunkyoung; Leverage, W Taylor; Liu, Yi; White, Ian M; Bentley, William E; Payne, Gregory F

2014-01-07

It is well-established that redox-reactions are integral to biology for energy harvesting (oxidative phosphorylation), immune defense (oxidative burst) and drug metabolism (phase I reactions), yet there is emerging evidence that redox may play broader roles in biology (e.g., redox signaling). A critical challenge is the need for tools that can probe biologically-relevant redox interactions simply, rapidly and without the need for a comprehensive suite of analytical methods. We propose that electrochemistry may provide such a tool. In this tutorial review, we describe recent studies with a redox-capacitor film that can serve as a bio-electrode interface that can accept, store and donate electrons from mediators commonly used in electrochemistry and also in biology. Specifically, we (i) describe the fabrication of this redox-capacitor from catechols and the polysaccharide chitosan, (ii) discuss the mechanistic basis for electron exchange, (iii) illustrate the properties of this redox-capacitor and its capabilities for promoting redox-communication between biology and electrodes, and (iv) suggest the potential for enlisting signal processing strategies to "extract" redox information. We believe these initial studies indicate broad possibilities for enlisting electrochemistry and signal processing to acquire "systems level" redox information from biology.

Multiscale Treatment for the Molecular Mechanism of a Diels-Alder Reaction in Solution: A QM/MM-MD Study.

Science.gov (United States)

Soto-Delgado, Jorge; Tapia, Ricardo A; Torras, Juan

2016-10-11

Thermodynamics and the solvent role in the acceleration of the Diels-Alder reaction between cyclopentadiene (CPD) and methyl vinyl ketone (MVK) have been revisited. In this work we use an ab initio hybrid QM/MM-MD scheme combined with multiple steered molecular dynamics to extract the free energy pofile in water and methanol using the bidirectional Minh-Adib estimator. We obtain 18.7 kcal mol -1 and 20.8 kcal mol -1 free energy barrier for the reaction in water and methanol, respectively. This methodology reproduces experimental values with an absolute error of about 0.8 kcal mol -1 . The experimental difference between the activation free-energy barriers of water and methanol is also reproduced with an absolute error of about 0.1 kcal mol -1 . We explore the charge transfer evolution along reaction coordinates to characterize the electronic behavior for this reaction. It is shown that the solvent molecules around the reaction system produce a global polarization along the reaction coordinate which is consistent with the solvent polarity. The results highlight the role of hydrogen bonding formed in the transition state to stabilize the system charge reorganization in the reaction process.

Immune Reactions Among Marine and Other Invertebrates

Science.gov (United States)

Bang, Frederik B.

1973-01-01

Discusses the defense mechanisms and immune reaction found in invertebrates, and examines the wealth of related biological problems that need study and many of the leads that have recently been developed. (JR)

Molecular eyes: proteins that transform light into biological information

NARCIS (Netherlands)

Kennis, J.T.M.; Mathes, T.

2013-01-01

Most biological photoreceptors are protein/cofactor complexes that induce a physiological reaction upon absorption of a photon. Therefore, these proteins represent signal converters that translate light into biological information. Researchers use this property to stimulate and study various

Solvent effects and potential of mean force study of the SN2 reaction of CH3+CN‑ in water

Science.gov (United States)

Li, Chen; Liu, Peng; Li, Yongfang; Wang, Dunyou

2018-03-01

We used a combined quantum mechanics and molecular mechanics (QM/MM) method to investigate the solvent effects and potential of mean force of the CH3F+CN‑ reaction in water. Comparing to gas phase, the water solution substantially affects the structures of the stationary points along the reaction path. We quantitatively obtained the solvent effects’ contributions to the reaction: 1.7 kcal/mol to the activation barrier and ‑26.0 kcal/mol to the reaction free energy. The potential mean of force calculated with the density functional theory/MM theory has a barrier height at 19.7 kcal/mol, consistent with the experimental result at 23.0 kcal/mol; the calculated reaction free energy at ‑43.5 kcal/mol is also consistent with the one estimated based on the gas-phase data at ‑39.7 kcal/mol. Project supported by the National Natural Science Foundation of China (Grant No. 11774206) and Taishan Scholarship Fund from Shandong Province, China.

Fiber coating/matrix reactions in silicon-base ceramic matrix composites

International Nuclear Information System (INIS)

Lee, K.N.; Jacobson, N.S.

1992-01-01

The Knudsen cell technique and coupons of carbon coated Si3N4 and BN coated SiC were employed to study the possible reactions at the SiC/C/Si3N4 and SiC/BN/SiC interface. Carbon reacts with Si3N4 to form gaseous N2 and solid SiC. Solid SiC acts as a physical barrier to the reaction, which prevents the generation of high N2 pressure predicted from thermochemical calculations. Thus, deleterious effects of the reaction to the composite are limited. Limited reactions between BN and C-rich SiC was observed. However, the vapor pressure was so low that it is not likely to cause any interfacial instability. The predicted formation of a BN-C solid solution was not observed. 10 refs

Fiber coating/matrix reactions in silicon-base ceramic matrix composites

Science.gov (United States)

Lee, K. N.; Jacobson, N. S.

1992-01-01

The Knudsen cell technique and coupons of carbon coated Si3N4 and BN coated SiC were employed to study the possible reactions at the SiC/C/Si3N4 and SiC/BN/SiC interface. Carbon reacts with Si3N4 to form gaseous N2 and solid SiC. Solid SiC acts as a physical barrier to the reaction, which prevents the generation of high N2 pressure predicted from thermochemical calculations. Thus, deleterious effects of the reaction to the composite are limited. Limited reactions between BN and C-rich SiC was observed. However, the vapor pressure was so low that it is not likely to cause any interfacial instability. The predicted formation of a BN-C solid solution was not observed.

Chemical memory reactions induced bursting dynamics in gene expression.

Science.gov (United States)

Tian, Tianhai

2013-01-01

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems.

Effects of ion and electron screening on thermonuclear reaction rates

International Nuclear Information System (INIS)

Brady, L.R. Jr.

1977-01-01

The effects of screening by ions and electrons on thermonuclear reaction rates in stellar plasmas are considered. The enhancement of the reaction rate ranges from negligible to extremely large (on the order of 10 26 or greater). In order to calculate these effects, the potential about a given reacting nucleus is determined. First, Boltzmann-Vlasov and Poisson-Boltzmann equations are solved to yield a Yukawa potential. A suitable approximation to this potential is integrated in the action integral to give the barrier penetration. The screened reaction rate is then found by the saddle-point method. In developing a general formalism to calculate the screened reaction rate and the screening factor, effects due to the finite size of the nucleus are considered and found to be negligible. An expression for the screening factor for resonant reaction rates is also derived. A different and relatively simple approach, based on work of Stewart and Pyatt (1966), is used to find the barrier penetration from the action integral in two approximations: a modified Coulomb potential and a constant-shift potential. Screening factors are calculated for carbon burning at T 6 = 100 and T 6 = 400 for a wide range of densities and also for several examples in late stellar evolution. These screening factors are, for the most part, greater than those given by most others by a few percent at low density to 4 or more orders of magnitude at T 6 = 100 and rho = 10 10 g/cm 3 . Near the edge of the crystalline lattice region, however, they are significantly lower than those of some others. The increase in reaction rates for carbon burning indicates that carbon ignition may occur at lower densities than previously thought and may affect the density at which a supernova shock may occur

Diffusion-controlled reactions modeling in Geant4-DNA

Energy Technology Data Exchange (ETDEWEB)

Karamitros, M., E-mail: matkara@gmail.com [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, INCIA, UMR 5287, F-33400 Talence (France); Luan, S. [University of New Mexico, Department of Computer Science, Albuquerque, NM (United States); Bernal, M.A. [Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, SP (Brazil); Allison, J. [Geant4 Associates International Ltd (United Kingdom); Baldacchino, G. [CEA Saclay, IRAMIS, LIDYL, Radiation Physical Chemistry Group, F-91191 Gif sur Yvette Cedex (France); CNRS, UMR3299, SIS2M, F-91191 Gif sur Yvette Cedex (France); Davidkova, M. [Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Francis, Z. [Saint Joseph University, Faculty of Sciences, Department of Physics, Mkalles, Beirut (Lebanon); Friedland, W. [Helmholtz Zentrum München, German Research Center for Environmental Health, Institute of Radiation Protection, Ingolstädter Landstr. 1, 85764 Neuherberg (Germany); Ivantchenko, V. [Ecoanalytica, 119899 Moscow (Russian Federation); Geant4 Associates International Ltd (United Kingdom); Ivantchenko, A. [Geant4 Associates International Ltd (United Kingdom); Mantero, A. [SwHaRD s.r.l., via Buccari 9, 16153 Genova (Italy); Nieminem, P.; Santin, G. [ESA-ESTEC, 2200 AG Noordwijk (Netherlands); Tran, H.N. [Division of Nuclear Physics and Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Stepan, V. [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Incerti, S., E-mail: incerti@cenbg.in2p3.fr [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France)

2014-10-01

Context Under irradiation, a biological system undergoes a cascade of chemical reactions that can lead to an alteration of its normal operation. There are different types of radiation and many competing reactions. As a result the kinetics of chemical species is extremely complex. The simulation becomes then a powerful tool which, by describing the basic principles of chemical reactions, can reveal the dynamics of the macroscopic system. To understand the dynamics of biological systems under radiation, since the 80s there have been on-going efforts carried out by several research groups to establish a mechanistic model that consists in describing all the physical, chemical and biological phenomena following the irradiation of single cells. This approach is generally divided into a succession of stages that follow each other in time: (1) the physical stage, where the ionizing particles interact directly with the biological material; (2) the physico-chemical stage, where the targeted molecules release their energy by dissociating, creating new chemical species; (3) the chemical stage, where the new chemical species interact with each other or with the biomolecules; (4) the biological stage, where the repairing mechanisms of the cell come into play. This article focuses on the modeling of the chemical stage. Method This article presents a general method of speeding-up chemical reaction simulations in fluids based on the Smoluchowski equation and Monte-Carlo methods, where all molecules are explicitly simulated and the solvent is treated as a continuum. The model describes diffusion-controlled reactions. This method has been implemented in Geant4-DNA. The keys to the new algorithm include: (1) the combination of a method to compute time steps dynamically with a Brownian bridge process to account for chemical reactions, which avoids costly fixed time step simulations; (2) a k–d tree data structure for quickly locating, for a given molecule, its closest reactants. The

ENGINEERED BARRIER SYSTEM: PHYSICAL AND CHEMICAL ENVIRONMENT

International Nuclear Information System (INIS)

R. Jarek

2005-01-01

The purpose of this model report is to describe the evolution of the physical and chemical environmental conditions within the waste emplacement drifts of the repository, including the drip shield and waste package surfaces. The resulting seepage evaporation and gas abstraction models are used in the total system performance assessment for the license application (TSPA-LA) to assess the performance of the engineered barrier system and the waste form. This report develops and documents a set of abstraction-level models that describe the engineered barrier system physical and chemical environment. Where possible, these models use information directly from other reports as input, which promotes integration among process models used for TSPA-LA. Specific tasks and activities of modeling the physical and chemical environment are included in ''Technical Work Plan for: Near-Field Environment and Transport In-Drift Geochemistry Model Report Integration'' (BSC 2005 [DIRS 173782], Section 1.2.2). As described in the technical work plan, the development of this report is coordinated with the development of other engineered barrier system reports. To be consistent with other project documents that address features, events, and processes (FEPs), Table 6.14.1 of the current report includes updates to FEP numbers and FEP subjects for two FEPs identified in the technical work plan (TWP) governing this report (BSC 2005 [DIRS 173782]). FEP 2.1.09.06.0A (Reduction-oxidation potential in EBS), as listed in Table 2 of the TWP (BSC 2005 [DIRS 173782]), has been updated in the current report to FEP 2.1.09.06.0B (Reduction-oxidation potential in Drifts; see Table 6.14-1). FEP 2.1.09.07.0A (Reaction kinetics in EBS), as listed in Table 2 of the TWP (BSC 2005 [DIRS 173782]), has been updated in the current report to FEP 2.1.09.07.0B (Reaction kinetics in Drifts; see Table 6.14-1). These deviations from the TWP are justified because they improve integration with FEPs documents. The updates

Hemoglobin and Myoglobin as Reducing Agents in Biological Systems. Redox Reactions of Globins with Copper and Iron Salts and Complexes.

Science.gov (United States)

Postnikova, G B; Shekhovtsova, E A

2016-12-01

In addition to reversible O2 binding, respiratory proteins of the globin family, hemoglobin (Hb) and myoglobin (Mb), participate in redox reactions with various metal complexes, including biologically significant ones, such as those of copper and iron. HbO 2 and MbO 2 are present in cells in large amounts and, as redox agents, can contribute to maintaining cell redox state and resisting oxidative stress. Divalent copper complexes with high redox potentials (E 0 , 200-600 mV) and high stability constants, such as [Cu(phen) 2 ] 2+ , [Cu(dmphen) 2 ] 2+ , and CuDTA oxidize ferrous heme proteins by the simple outer-sphere electron transfer mechanism through overlapping π-orbitals of the heme and the copper complex. Weaker oxidants, such as Cu2+, CuEDTA, CuNTA, CuCit, CuATP, and CuHis (E 0 ≤ 100-150 mV) react with HbO 2 and MbO 2 through preliminary binding to the protein with substitution of the metal ligands with protein groups and subsequent intramolecular electron transfer in the complex (the site-specific outer-sphere electron transfer mechanism). Oxidation of HbO 2 and MbO 2 by potassium ferricyanide and Fe(3) complexes with NTA, EDTA, CDTA, ATP, 2,3-DPG, citrate, and pyrophosphate PP i proceeds mainly through the simple outer-sphere electron transfer mechanism via the exposed heme edge. According to Marcus theory, the rate of this reaction correlates with the difference in redox potentials of the reagents and their self-exchange rates. For charged reagents, the reaction may be preceded by their nonspecific binding to the protein due to electrostatic interactions. The reactions of LbO 2 with carboxylate Fe complexes, unlike its reactions with ferricyanide, occur via the site-specific outer-sphere electron transfer mechanism, even though the same reagents oxidize structurally similar MbO 2 and cytochrome b 5 via the simple outer-sphere electron transfer mechanism. Of particular biological interest is HbO 2 and MbO 2 transformation into met-forms in the presence

The breakdown of vinyl ethers as a two-center synchronous reaction

Science.gov (United States)

Pokidova, T. S.; Shestakov, A. F.

2009-11-01

The experimental data on the molecular decomposition of vinyl ethers of various structures to alkanes and the corresponding aldehydes or ketones in the gas phase were analyzed using the method of intersecting parabolas. The enthalpies and kinetic parameters of decomposition were calculated for 17 reactions. The breakdown of ethers is a two-center concerted reaction characterized by a very high classical potential barrier to the thermally neutral reaction (180-190 kJ/mol). The kinetic parameters (activation energies and rate constants) of back reactions of the formation of vinyl ethers in the addition of aldehydes or ketones to alkanes were calculated using the method of intersecting parabolas. The factors that influenced the activation energy of the decomposition and formation of ethers were discussed. Quantum-chemical calculations of several vinyl ether decomposition reactions were performed. Ether formation reactions were compared with the formation of unsaturated alcohols as competitive reactions, which can occur in the interaction of carbonyl compounds with alkenes.

A new barrier potential and alpha-decay half-lives of even–even nuclei in the 82⩽Z⩽92 regime

Energy Technology Data Exchange (ETDEWEB)

Hassanabadi, Hasan [Physics Department, Shahrood University of Technology, Shahrood (Iran, Islamic Republic of); Javadimanesh, ELham, E-mail: elham_javadimanesh89@yahoo.com [Department of Basic Sciences, Shahrood Branch, Islamic Azad University, Shahrood (Iran, Islamic Republic of); Zarrinkamar, Saber [Department of Basic Sciences, Garmsar Branch, Islamic Azad University, Garmsar (Iran, Islamic Republic of)

2013-05-15

The alpha-decay half-life in a nuclear reaction is mainly affected by the penetration probability, which itself depends on the choice of the barrier potential. Here, we propose a new barrier potential to investigate the alpha-decay half-lives in the even–even nuclei from {sup 178}Po to {sup 238}U. The obtained results are motivating.